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WO2014098222A1 - Film stratifié, feuille arrière de module de cellules solaires et module de cellules solaires - Google Patents

Film stratifié, feuille arrière de module de cellules solaires et module de cellules solaires Download PDF

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Publication number
WO2014098222A1
WO2014098222A1 PCT/JP2013/084265 JP2013084265W WO2014098222A1 WO 2014098222 A1 WO2014098222 A1 WO 2014098222A1 JP 2013084265 W JP2013084265 W JP 2013084265W WO 2014098222 A1 WO2014098222 A1 WO 2014098222A1
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polyester
polymer layer
polyester film
film
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Japanese (ja)
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福田　誠
上平　茂生
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • H10F19/85—Protective back sheets
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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 laminated film, a back sheet for a solar cell module, and a solar cell module.
  • a solar cell module generally has a structure in which glass or a front sheet / transparent filling material (sealing material) / solar cell element / sealing material / back sheet are laminated in this order from the light-receiving surface side where sunlight enters. is doing.
  • the solar cell element is generally embedded in a resin (sealing material) such as EVA (ethylene-vinyl acetate copolymer), and further has a structure in which a protective sheet for solar cell is attached thereon.
  • the solar cell module back sheet disposed in the outermost layer particularly serves to protect the solar cell elements.
  • a polyester film particularly a polyethylene terephthalate (hereinafter referred to as PET) film has been used for a back sheet for a solar cell module.
  • PET polyethylene terephthalate
  • the polyester film has excellent heat resistance, mechanical properties, chemical resistance, and the like, it is preferably used for a back sheet for a solar cell module.
  • these films have poor hydrolysis resistance, the molecular weight decreases due to hydrolysis, and the mechanical properties deteriorate due to progress of embrittlement. Therefore, these films can be used as back sheets for solar cells over a long period of time. The practical strength could not be maintained.
  • Patent Documents 1 and 2 suggest that a ketene imine compound is added to the polyester film as an end-capping agent.
  • the ketene imine compound functions to suppress hydrolysis of the polyester by reacting with the terminal carboxyl group of the polyester.
  • the present inventors suppressed the crying of the ketene compound when the polymer layer is laminated on the polyester film containing the ketene imine compound, and has high adhesion. Studies were conducted with the aim of providing a laminated film that can be used.
  • the present inventors laminated a polymer layer containing a binder having a specific functional group on a polyester film containing a ketene imine compound having a specific structure.
  • a polymer layer containing a binder having a specific functional group on a polyester film containing a ketene imine compound having a specific structure.
  • the present inventors can maintain good adhesion between the polymer layer and the adherend laminated thereon.
  • the headline and the present invention have been completed. Specifically, the present invention has the following configuration.
  • a laminated film comprising a polyester film and a polymer layer laminated adjacent to at least one surface of the polyester film, wherein the polyester film is represented by the following general formula (1): Wherein the polymer layer has at least one functional group selected from a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilyl group.
  • a laminated film comprising a binder having a group.
  • R 1 and R 2 each independently represents an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group, and R 3 represents an alkyl group or an aryl group.
  • R 11 to R 20 each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group. R 11 to R 20 may combine with each other to form a ring.
  • R 3 represents an alkyl group or an aryl group.
  • the polymer layer described above includes a binder having at least one functional group selected from a carboxyl group, an epoxy group, and an alkoxysilyl group, according to [1] or [2] Laminated film.
  • R 1 and R 2 each independently represents an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group
  • R 3 represents an alkyl group or an aryl group.
  • R 1 and R 2 each independently represents an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group, and R 3 represents an alkyl group or an aryl group.
  • a ketene compound starts to cry on the surface of a polymer layer by laminating a polymer layer containing a binder having a specific functional group on a polyester film containing a ketene imine compound having a specific structure. This can be suppressed. Thereby, the adhesiveness of a polymer layer and a polyester film can be improved. Furthermore, the adhesion between the polymer layer and the adherend laminated thereon can also be improved.
  • the laminated film in which a polyester film and a polymer layer are laminated is placed under severe conditions of high temperature and high humidity, the ketene compound is prevented from crying on the surface of the polymer layer. Therefore, the adhesion of the laminated film can be maintained over a long period of time. For this reason, the laminated
  • FIG. 1 is a cross-sectional view showing an example of the laminated film of the present invention.
  • FIG. 2 is a cross-sectional view showing a state in which the laminated film of the present invention is bonded to an adherend such as an EVA film.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the present invention relates to a laminated film including a polyester film and a polymer layer laminated adjacent to at least one surface of the polyester film.
  • the polyester film includes polyester and a ketene imine compound represented by the following general formula (1)
  • the polymer layer includes a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, an isocyanate group, an epoxy group, and a silanol group.
  • a binder having at least one functional group selected from alkoxysilyl groups.
  • R 1 and R 2 each independently represents an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group
  • R 3 represents an alkyl group or an aryl group.
  • the ketene compound produced in the polyester film can be prevented from crying on the surface of the polymer layer. Furthermore, in the present invention, crying of the ketene compound can be suppressed even when the laminated film is placed under severe conditions of high temperature and high humidity. Thereby, the adhesiveness of a polymer layer and a polyester film can be improved, and also the adhesiveness between the laminated film stuck via a polymer layer and an adherend can be improved. In particular, when the laminated film is used as a back sheet for a solar cell module, the adhesion between the laminated film and the EVA film can be improved, which is preferable.
  • FIG. 1 shows an example of a laminated film 10 according to the present invention.
  • a laminated film 10 shown in FIG. 1 has a two-layer structure in which a polyester film 2 and a polymer layer 3 are laminated on one surface of the polyester film 2.
  • the polymer layer 3 may be provided in both surfaces of the polyester film 2, and another layer may be provided.
  • FIG. 2 shows a state in which the laminated film 10 is bonded to the EVA film 5 that is a member of the solar cell module.
  • the ketene compound is liberated in the polyester film 2 containing the ketene imine compound, and the ketene compound is not only at the interface between the polymer layer 3 and the polyester film 2 but also at the interface between the polymer layer 3 and the EVA film 5. It was spreading until. Such diffusion of the ketene compound is called crying of the ketene compound.
  • the polymer layer 3 has at least one functional group selected from among a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilyl group. Since the binder is included, diffusion of the ketene compound can be suppressed. This is considered that the above-mentioned binder adsorbs the ketene compound to prevent the ketene compound from crying out on the interface between the polymer layer 3 and the EVA film 5.
  • the laminated film of the present invention can suppress crying of the ketene compound even under high temperature and high humidity conditions. For this reason, the laminated film of the present invention is particularly suitably used for a solar cell module that is often used under severe conditions of high temperature and high humidity.
  • the laminated film of the present invention has a polyester film as a support.
  • the polyester film used in the present invention contains polyester and a ketene imine compound.
  • a ketene imine compound if the ketene imine compound as represented by the said General formula (1) can be contained, it is. For this reason, the polyester film has excellent hydrolysis resistance.
  • the thickness of the polyester film of the present invention varies depending on the application, but when used as a member of a back sheet for a solar cell module, it is preferably 25 to 300 ⁇ m, more preferably 120 to 300 ⁇ m.
  • the thickness of the polyester film By setting the thickness of the polyester film to the above lower limit value or more, sufficient mechanical strength can be obtained, and by making the thickness not more than the above upper limit value, a merit in cost can be obtained.
  • the polyester film of the present invention is preferably stretched, more preferably biaxially stretched, and plane biaxially stretched is particularly preferable as compared with stretching such as tubular, and sequential biaxial stretching. It is particularly preferred that
  • the polyester film may contain other additives without departing from the gist of the present invention, and examples of the additives include antioxidants and ultraviolet inhibitors.
  • polyester film used in the present invention contains polyester.
  • the kind in particular of polyester is not restrict
  • the polyester is preferably a saturated polyester.
  • a saturated polyester by using a saturated polyester, a polyester film that is superior in terms of mechanical strength as compared with a film using an unsaturated polyester can be obtained.
  • the polyester include a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
  • linear saturated polyester examples include polyethylene terephthalate (PET), polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), and polyethylene-2,6-naphthalate.
  • PET polyethylene terephthalate
  • PEN polyethylene-2,6-naphthalate
  • the polyester may be a homopolymer or a copolymer. Further, polyester may be blended with a small amount of other types of resin, such as polyimide. Further, as the polyester, a crystalline polyester capable of forming anisotropy when melted may be used.
  • the molecular weight of the polyester is preferably 5000 to 30000, more preferably 8000 to 26000, and particularly preferably 12000 to 24000 from the viewpoint of heat resistance and viscosity.
  • a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent can be used.
  • the polyester can be obtained by reacting a dicarboxylic acid or an ester-forming derivative thereof with a low molecular weight aliphatic diol or a high molecular weight diol.
  • the dicarboxylic acid or its ester-forming derivative include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, paraphenylene dicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, dimethyl orthophthalate, dimethyl naphthalene dicarboxylate, and paraphenylene. And dimethyl dicarboxylate. These may be used alone or in combination of two or more.
  • Examples of the low molecular weight aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentane. Examples thereof include diol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like. These may be used alone or in combination of two or more.
  • Examples of the high molecular weight diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like. These may be used alone or in combination of two or more.
  • Examples of the crystalline polyester composed of the above components include polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, butanediol terephthalate polytetramethylene glycol copolymer, and the like. . These may be used alone or in combination of two or more. Particularly preferred among aromatic polyesters are those using terephthalic acid and naphthalenedicarboxylic acid as main components as dicarboxylic acids, and those having ethylene glycol and cyclohexanedimethanol as main components as diols, more preferably polyethylene terephthalate. Polyethylene naphthalate and polycyclohexanedimethylene terephthalate, more preferably polyethylene terephthalate and polyethylene naphthalate.
  • Polyester can be synthesized by a known method.
  • polyester can be synthesized by a known polycondensation method or ring-opening polymerization method, and any of transesterification and direct polymerization can be applied.
  • the polyester used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof
  • An aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof can be produced by an esterification reaction or an ester exchange reaction and then a polycondensation reaction.
  • the carboxylic acid value and intrinsic viscosity of the polyester can be controlled by selecting the raw material and reaction conditions. In order to effectively advance the esterification reaction or transesterification reaction and polycondensation reaction, it is preferable to add a polymerization catalyst during these reactions.
  • the polymerization catalyst for polymerizing the polyester Sb-based, Ge-based, and Ti-based compounds are preferably used from the viewpoint of suppressing the carboxyl group content to a predetermined range or less, and Ti-based compounds are particularly preferable.
  • Ti-based compounds an embodiment in which polymerization is performed by using the Ti compound as a catalyst in the range of 1 to 30 ppm, more preferably 3 to 15 ppm is preferable.
  • the proportion of the Ti-based compound is within the above range, the terminal carboxyl group can be adjusted to the following range, and the hydrolysis resistance of the polymer substrate can be kept low.
  • Examples of the synthesis of polyester using a Ti compound include Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 397756, and Japanese Patent No. 396226. Gazette, Japanese Patent No. 3997866, Japanese Patent No. 3996871, Japanese Patent No. 40000867, Japanese Patent No. 4053837, Japanese Patent No. 4127119, Japanese Patent No. 4134710, Japanese Patent No. 4159154, Japanese Patent No. 4269704, The method described in Japanese Patent No. 431538 can be applied.
  • the polyester is preferably solid-phase polymerized after polymerization.
  • Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time and then sent out), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time).
  • Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523 are disclosed. No. 3,717,392, and Japanese Patent No. 4,167,159 can be applied.
  • the temperature of the solid phase polymerization is preferably 170 to 240 ° C, more preferably 180 to 230 ° C, and further preferably 190 to 220 ° C.
  • the solid phase polymerization time is preferably 5 to 100 hours, more preferably 10 to 75 hours, and further preferably 15 to 50 hours.
  • the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
  • the polyester film of the present invention contains a ketene imine compound.
  • the ketene imine compound may be used alone or in combination with other end-capping agents such as carbodiimide compounds.
  • a ketene imine compound represented by the following general formula (1) is preferably used as the ketene imine compound.
  • the ketene imine compound represented by the following general formula (1) will be described.
  • R 1 and R 2 each independently represents an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group
  • R 3 represents an alkyl group or an aryl group.
  • the aryl group represented by R 1 and R 2 is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
  • Examples of the aryl group represented by R 1 and R 2 include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable.
  • the aryl group includes a heteroaryl group.
  • the heteroaryl group refers to a group in which at least one of the ring-constituting atoms of a 5-membered, 6-membered or 7-membered ring exhibiting aromaticity or its condensed ring is substituted with a heteroatom.
  • heteroaryl group examples include imidazolyl group, pyridyl group, quinolyl group, furyl group, thienyl group, benzoxazolyl group, indolyl group, benzimidazolyl group, benzthiazolyl group, carbazolyl group, and azepinyl group.
  • the hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and particularly preferably an oxygen atom or a nitrogen atom.
  • the aryl group or heteroaryl group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • the carbon number of the aryl group or heteroaryl group represented by R 1 and R 2 is the number of carbons not including a substituent.
  • the aryloxy group represented by R 1 and R 2 is preferably an aryloxy group having 6 to 20 carbon atoms, and more preferably an aryloxy group having 6 to 12 carbon atoms.
  • Examples of the aryl moiety of the aryloxy group represented by R 1 and R 2 include the examples of the aryl group or heteroaryl group described above.
  • the aryloxy group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • carbon number of the aryloxy group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • the arylaminocarbonyl group represented by R 1 and R 2 is preferably an arylaminocarbonyl group having 6 to 20 carbon atoms.
  • Preferable examples of the arylamino moiety of the arylaminocarbonyl group having 6 to 20 carbon atoms include a group in which —NH— is linked to the terminal of the aryl group represented by R 1 and R 2 .
  • Examples of the aryl moiety of the arylaminocarbonyl group represented by R 1 and R 2 include the examples of the aryl group or heteroaryl group described above.
  • the arylaminocarbonyl group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • carbon number of the arylaminocarbonyl group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • Aryloxycarbonyl group represented by R 1 and R 2 is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, more preferably R 1 and be an aryloxycarbonyl group having 7 to 12 carbon atoms
  • Examples of the aryl moiety of the aryloxycarbonyl group represented by R 2 include the above-described aryl groups and heteroaryl groups.
  • the aryloxycarbonyl group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • the carbon number of the aryloxycarbonyl group which R ⁇ 1 > and R ⁇ 2 > represent shows the carbon number which does not contain a substituent.
  • R 1 and R 2 each independently represents an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group, but the ketene imine represented by the general formula (1)
  • the compound may be used in combination with a ketene imine compound in which R 1 and R 2 are an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aminocarbonyl group, or an acyl group.
  • the ratio of the ketene imine compound represented by the general formula (1) to the total amount of the ketene imine compound is preferably 80% or more, more preferably 90% or more, and 100%. Is particularly preferred.
  • the alkyl group represented by R 1 and R 2 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group represented by R 1 and R 2 may be linear, branched or cyclic.
  • Examples of the alkyl group represented by R 1 and R 2 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, n- A pentyl group, a sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, a cyclohexyl group, and the like can be given.
  • a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, and a cyclohexyl group are more preferable.
  • the alkyl group represented by R 1 and R 2 may further have a substituent. Unless the reactivity of a ketene imine group and a carboxyl group is lowered, the substituent is not particularly limited, and the above substituents can be exemplified similarly.
  • carbon number of the alkyl group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • the alkoxy group represented by R 1 and R 2 is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms. It is particularly preferred that The alkoxy group represented by R 1 and R 2 may be linear, branched or cyclic. Preferable examples of the alkoxy group represented by R 1 and R 2 include a group in which —O— is linked to the terminal of the alkyl group represented by R 1 and R 2 .
  • the alkoxy group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • carbon number of the alkoxy group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • the alkoxycarbonyl group represented by R 1 and R 2 is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, and 2 to 6 carbon atoms. Particularly preferred is an alkoxycarbonyl group.
  • Examples of the alkoxy moiety of the alkoxycarbonyl group represented by R 1 and R 2 include the examples of the alkoxy group described above.
  • the alkoxycarbonyl group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • carbon number of the alkoxycarbonyl group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • the aminocarbonyl group represented by R 1 and R 2 is preferably an alkylaminocarbonyl group having 1 to 20 carbon atoms, more preferably an alkylaminocarbonyl group having 2 to 12 carbon atoms, and a carbon number of 2 Particularly preferred is an alkylaminocarbonyl group of ⁇ 6.
  • Preferable examples of the alkylamino part of the alkylaminocarbonyl group include groups in which —NH— is linked to the terminal of the alkyl group represented by R 1 and R 2 .
  • the alkylaminocarbonyl group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • carbon number of the alkylaminocarbonyl group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • the acyl group represented by R 1 and R 2 is preferably an acyl group having 2 to 20 carbon atoms, more preferably an acyl group having 2 to 12 carbon atoms, and an acyl group having 2 to 6 carbon atoms. It is particularly preferred that The acyl group represented by R 1 and R 2 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered. In addition, carbon number of the acyl group which R ⁇ 1 > and R ⁇ 2 > represent shows carbon number which does not contain a substituent.
  • R 3 represents an alkyl group or an aryl group.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group represented by R 3 may be linear, branched or cyclic.
  • Examples of the alkyl group represented by R 3 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, n-pentyl group, Examples thereof include a sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, and a cyclohexyl group.
  • a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a cyclohexyl group are more preferable.
  • the alkyl group represented by R 3 may further have a substituent. Unless the reactivity of a ketene imine group and a carboxyl group is lowered, the substituent is not particularly limited, and the above substituents can be exemplified similarly.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
  • Examples of the aryl group represented by R 3 include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable.
  • the aryl group includes a heteroaryl group.
  • the heteroaryl group refers to a group in which at least one of the ring-constituting atoms of a 5-membered, 6-membered or 7-membered ring exhibiting aromaticity or its condensed ring is substituted with a heteroatom.
  • heteroaryl group examples include imidazolyl group, pyridyl group, quinolyl group, furyl group, thienyl group, benzoxazolyl group, indolyl group, benzimidazolyl group, benzthiazolyl group, carbazolyl group, and azepinyl group.
  • the hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and particularly preferably an oxygen atom or a nitrogen atom.
  • the aryl group or heteroaryl group represented by R 3 may further have a substituent, and the substituent is not particularly limited as long as the reactivity between the ketene imine group and the carboxyl group is not lowered.
  • General formula (1) may contain the repeating unit.
  • at least one of R 1 and R 3 is a repeating unit, and this repeating unit preferably contains a ketene imine moiety.
  • the molecular weight of the portion excluding the nitrogen atom constituting the ketene imine of the ketene imine compound and the substituent bonded to the nitrogen atom is preferably 320 or more. That is, in the general formula (1), the molecular weight of the R 1 —C ( ⁇ C) —R 2 group is preferably 320 or more.
  • the molecular weight of the portion excluding the nitrogen atom of the ketene imine compound and the substituent bonded to the nitrogen atom is preferably 320 or more, more preferably 500 to 1500, and still more preferably 600 to 1000. .
  • the ketene imine compound and the ketene compound are stably present in the polyester film by setting the molecular weight of the portion excluding the nitrogen atom constituting the ketene imine and the substituent bonded to the nitrogen atom within the above range. be able to.
  • the ketene imine compound by setting the ketene imine compound to a certain molecular weight, not only the ketene compound is volatilized but also the volatilization of the ketene imine compound can be suppressed in the process of forming a polyester film.
  • adhesiveness with a polymer layer can be improved. This is because when the ketene imine compound has a molecular weight within a certain range, the polyester terminal can be made bulky, and the polyester terminal diffuses into the polymer layer and exhibits the anchoring effect.
  • ketene imine compound it is preferable to use a ketene imine compound represented by the following general formula (2).
  • ketene imine compound represented by the following general formula (2) will be described.
  • R 11 to R 20 each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group.
  • R 11 to R 20 may be bonded to each other to form a ring.
  • R 3 represents an alkyl group or an aryl group.
  • R 11 to R 20 each independently represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms.
  • a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable, and a hydrogen atom is particularly preferable.
  • the alkyl group represented by R 11 to R 20 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 2 to 6 carbon atoms. It is particularly preferred.
  • the alkyl group represented by R 11 to R 20 may be linear, branched or cyclic.
  • Examples of the alkyl group represented by R 11 to R 20 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, n- A pentyl group, a sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, a cyclohexyl group, and the like can be given.
  • a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, and a cyclohexyl group are more preferable.
  • the aryl group represented by R 11 to R 20 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and an aryl group having 6 carbon atoms. Particularly preferred.
  • Examples of the aryl group represented by R 11 to R 20 include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable.
  • the aryl group includes a heteroaryl group.
  • the heteroaryl group refers to a group in which at least one of the ring-constituting atoms of a 5-membered, 6-membered or 7-membered ring exhibiting aromaticity or its condensed ring is substituted with a heteroatom.
  • the heteroaryl group include imidazolyl group, pyridyl group, quinolyl group, furyl group, thienyl group, benzoxazolyl group, indolyl group, benzimidazolyl group, benzthiazolyl group, carbazolyl group, and azepinyl group.
  • the hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and particularly preferably an oxygen atom or a nitrogen atom.
  • the alkoxy group represented by R 11 to R 20 is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms. It is particularly preferred.
  • the alkoxy group represented by R 1 and R 5 may be linear, branched or cyclic.
  • Preferable examples of the alkoxy group represented by R 11 to R 20 include a group in which —O— is linked to the terminal of the alkyl group represented by R 11 to R 20 .
  • the alkyl group, aryl group or alkoxy group represented by R 11 to R 20 may further have a substituent, and the substituent is not particularly limited.
  • R 11 to R 20 may combine with each other to form a ring.
  • the ring formed at this time is not particularly limited, but is preferably an aromatic ring.
  • two or more of R 11 to R 15 may be bonded to each other to form a condensed ring, and an arylene group or heteroarylene group having 10 or more carbon atoms is formed together with the benzene ring substituted by R 11 to R 15. May be.
  • the arylene group having 10 or more carbon atoms formed at this time include aromatic groups having 10 to 15 carbon atoms such as naphthalenediyl group.
  • R 16 to R 20 may be bonded to each other to form a condensed ring, and an arylene group or heteroarylene having 10 or more carbon atoms together with a benzene ring substituted by R 16 to R 20.
  • a preferred range at that time is the same as the preferred range when an arylene group or heteroarylene group having 10 or more carbon atoms is formed together with the benzene ring substituted by R 16 to R 20 .
  • R 11 to R 20 are not bonded to each other to form a ring.
  • ketene imine compound a ketene imine compound represented by the following general formula (3) may be used.
  • the ketene imine compound represented by the following general formula (3) will be described.
  • R 1 is preferably an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group, and is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aminocarbonyl group, or an acyl group. It may be a group.
  • R 2 is preferably an aryl group having L 1 as a substituent, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group, and an alkyl group, an alkoxy group, an alkoxycarbonyl group having L 1 as a substituent, It may be an aminocarbonyl group or an acyl group.
  • R 3 represents an alkyl group or an aryl group.
  • n represents an integer of 1 to 4
  • L 1 represents an n-valent linking group.
  • the molecular weight of the (R 1 —C ( ⁇ C) —R 2 —) nL 1 group is preferably 320 or more.
  • R 1 is the same as that in general formula (1), and the preferred range is also the same.
  • R 2 represents an aryl group having L 1 is an n-valent linking group, aryloxy group, arylamino group or preferably an aryloxycarbonyl group,, L 1 as a substituent
  • the aryl group, aryloxy group, arylaminocarbonyl group, aryloxycarbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aminocarbonyl group or acyl group are the same as those in the general formula (1), and the preferred range is also It is the same.
  • R 3 is the same as that in general formula (1), and the preferred range is also the same.
  • L 1 represents an n-valent linking group, where n represents an integer of 1 to 4. Among these, n is preferably 2 to 4.
  • the divalent linking group include, for example, —NR 8 — (R 8 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, A hydrogen atom is preferable), —SO 2 —, —CO—, substituted or unsubstituted alkylene group, substituted or unsubstituted alkenylene group, alkynylene group, substituted or unsubstituted phenylene group, substituted or unsubstituted Examples thereof include a substituted biphenylene group, a substituted or unsubstituted naphthylene group, —O—, —S— and —SO—, and a group obtained by combining two or more thereof.
  • the trivalent linking group examples include a group obtained by removing one hydrogen atom from those having a substituent among the linking groups mentioned as examples of the divalent linking group.
  • Specific examples of the tetravalent linking group include, for example, a group obtained by removing two hydrogen atoms from those having a substituent among the linking groups mentioned as examples of the divalent linking group.
  • n 2 to 4
  • a compound having two or more ketene imine moieties in one molecule can be obtained, and a more excellent end-capping effect can be exhibited.
  • the molecular weight per ketene imine group can be lowered, and the ketene imine compound and the terminal carboxyl group of the polyester can be reacted efficiently. Furthermore, it can suppress that a ketene imine compound and a ketene compound volatilize by having two or more ketene imine parts in 1 molecule.
  • n is more preferably 3 or 4.
  • n is more preferably 3 or 4.
  • ketene imine compound a ketene imine compound represented by the following general formula (4) may be used.
  • the ketene imine compound represented by the following general formula (4) will be described.
  • R 1 and R 5 are preferably an aryl group, an aryloxy group, an arylaminocarbonyl group, or an aryloxycarbonyl group, and are an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aminocarbonyl group, or It may be an acyl group.
  • R 2 and R 4 are aryl groups having L 2 as a substituent group, an aryloxy group, an arylamino group or preferably an aryloxycarbonyl group, an alkyl group having L 2 as a substituent group, an alkoxy group, an alkoxy It may be a carbonyl group, an aminocarbonyl group or an acyl group.
  • R 3 and R 6 represent an alkyl group or an aryl group.
  • L 2 represents a single bond or a divalent linking group.
  • the molecular weight of the R 1 —C ( ⁇ C) —R 2 —L 2 —R 4 —C ( ⁇ C) —R 5 group is preferably 320 or more.
  • R 1 is the same as that in general formula (1), and the preferred range is also the same.
  • R 5 is the same as R 1 in the general formula (1), and the preferred range is also the same.
  • R 2 is the same as that in general formula (3), and the preferred range is also the same.
  • R 4 is the same as R 2 in formula (3), and the preferred range is also the same.
  • R 3 is the same as that in general formula (1), and the preferred range is also the same.
  • R 6 is the same as R 3 in the general formula (1), and the preferred range is also the same.
  • L 2 represents a single bond or a divalent linking group.
  • divalent linking group include the linking groups exemplified for L 1 in formula (3).
  • the ketene imine compound of the present invention is a compound having at least one ketene imine group.
  • the ketene imine compound is preferably added in an amount of 0.05 to 5% by mass, more preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass with respect to the polyester. It is more preferable to add so that it may become%.
  • the hydrolysis resistance of a polyester film can be effectively improved by making the addition rate of a ketene imine compound into the said range.
  • the polyester film of the present invention does not refuse to contain a ketene imine compound other than the ketene imine compound of the present invention unless it is contrary to the spirit of the present invention, but 90% of the ketene imine compound contained in the polyester film of the present invention.
  • the above is preferably the ketene imine compound of the present invention, 95% or more is more preferably the ketene imine compound of the present invention, and 100% is particularly preferably the ketene imine compound of the present invention.
  • the ketene imine compound is preferably reacted in an amount of 5 to 99%, preferably 10 to 90%, more preferably 20 to 80%. If the reaction rate is too low, the hydrolysis resistance is deteriorated. If the reactivity is too high, the viscosity may increase and film formation may be difficult.
  • the reaction rate of the ketene imine compound can be obtained from the IR spectrum of the polyester film and can be calculated from the peak at 2000 cm ⁇ 1 .
  • the laminated film of the present invention has a polymer layer.
  • the polymer layer used in the present invention is provided on at least one surface of the above-described polyester film, and functions as an easy adhesion layer that bonds the polyester film and the EVA film.
  • the polymer layer includes a binder having at least one functional group selected from among a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilyl group.
  • binders react with the ketene compound in the polymer layer and function to adsorb the ketene compound. For this reason, in the polyester film, the ketene compound produced
  • binder among the binders described above, those having at least one selected from a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, an epoxy group and an alkoxysilyl group as a functional group are more preferably used. Those having a group as a functional group are particularly preferably used. Since the binder having these functional groups easily adsorbs to the ketene compound in the polymer layer, the ketene compound can be effectively prevented from crying out on the surface of the polymer layer.
  • the binder having a specific functional group as described above is preferably contained in an amount of 0.1 to 1000 parts by weight, and 0.5 to 800 parts by weight, based on 100 parts by weight of the ketene imine compound contained in the polyester film. More preferably, it is contained in an amount of 1 to 500 parts by mass.
  • the number of functional groups contained in the binder is preferably 1 to 99 mol%, preferably 5 to 50 mol%, more preferably 5 to 40 mol% per molecule.
  • the binder having a specific functional group as described above is preferably composed of polyolefin, polyacryl, polyurethane, polyester, or rubber resin. Such a binder can be obtained by homopolymerizing or copolymerizing a monomer having a specific functional group.
  • polyolefin resin As the polyolefin resin, it is also preferable to use a polyvinyl alcohol (PVA) resin. This is because when the polyester film produced according to the present invention is used as a solar battery back sheet, if a polymer layer containing a PVA resin is provided, it has a high affinity with the polyvinyl alcohol resin laminated on the polymer layer. is there. As an example of a commercial item, PVA105 (Kuraray Co., Ltd. product) etc. are mentioned. Moreover, as polyolefin resin other than PVA, a modified polyolefin copolymer is preferable, for example. Commercially available products on the market may be used as the above-mentioned polyolefin resin.
  • PVA polyvinyl alcohol
  • Arrow Base SE-1013N For example, Arrow Base SE-1013N, SD-1010, TC-4010, TD-4010 (manufactured by Unitika Ltd.), Hitech S3148, S3121, S8512 (manufactured by Toho Chemical Co., Ltd.), Chemipearl S-120, S-75N, V100, EV210H (manufactured by Mitsui Chemicals, Inc.) and the like.
  • Arrow Base SE-1013N manufactured by Unitika Co., Ltd., which is a terpolymer of low density polyethylene, acrylic acid ester, and maleic anhydride. .
  • polyester resins for example, Vylonal MD-1245 (manufactured by Toyobo Co., Ltd.)
  • a polyurethane resin for example, a carbonate-based urethane resin is preferable.
  • Superflex 460 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • These polyolefin resins may be used alone or in combination of two or more. When two or more of these polyolefin resins are used in combination, a combination of an acrylic resin and a polyolefin resin is preferable.
  • Polyacryl is obtained by copolymerizing the monomers exemplified below. That is, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, etc.); Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; acrylic acid and methacrylic acid Carboxylic acids such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and its
  • acrylic resins examples include Julimer ET-410, SEK-301 (manufactured by Nippon Pure Chemical Industries, Ltd.) and the like.
  • the composite resin of acrylic and silicone examples include Ceranate WSA1060, WSA1070 (manufactured by DIC Corporation), H7620, H7630, H7650 (manufactured by Asahi Kasei Chemicals Corporation) and the like.
  • Nipol SX1105 made by Nippon Zeon Co., Ltd.
  • Nipol SX1105 made by Nippon Zeon Co., Ltd.
  • Polyurethane resin is composed of polyol, polyisocyanate, chain extender, crosslinking agent and the like.
  • polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyethers such as polyoxytetramethylene glycol, polyethylene adipate, polyethylene-butylene adipate, polycaprolactone, and the like by dehydration reaction of dicarboxylic acid.
  • polyesters to be produced polycarbonates having a carbonate bond, acrylic polyols, castor oil and the like.
  • polyisocyanates examples include tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
  • chain extenders or crosslinking agents examples include ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodicyclohexylmethane, Water etc. are mentioned.
  • polyester resin examples include polyester resins obtained by polymerizing polyester monomers as exemplified below.
  • polyester the polyester obtained from the following polybasic acid component and diol component can be used.
  • the polyvalent base component examples include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, Examples include pyromellitic acid, dimer acid, and 5-sodium sulfoisophthalic acid.
  • polyester constituting the polymer binder it is preferable to use a copolymerized polyester using two or more kinds of dicarboxylic acid components.
  • the polyester may contain an unsaturated polybasic acid component such as maleic acid or itaconic acid, or a hydroxycarboxylic acid component such as p-hydroxybenzoic acid, if it is in a slight amount.
  • Polyester diol components include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, dimethylolpropane, and the like, poly (ethylene oxide) ) Glycol and poly (tetramethylene oxide) glycol.
  • the polymer layer may further contain a wetting agent, an antistatic agent, a coloring agent, a surfactant, an ultraviolet absorber and the like.
  • a wetting agent an antistatic agent, a coloring agent, a surfactant, an ultraviolet absorber and the like.
  • the content is, for example, 1 to 20% by mass with respect to the solid content.
  • the thickness of the polymer layer is 10 to 500 nm.
  • the thickness of the polymer layer may be 10 to 500 nm, preferably 20 to 300 nm, and more preferably 30 to 120 nm.
  • the thickness of a polymer layer means the average film thickness of a polymer layer.
  • an unstretched polyester film can be formed by cooling and solidifying a melt obtained by melting the mixture used in the present invention and the ketene imine compound described above.
  • the melting temperature at the time of melting is preferably 120 to 350 ° C., more preferably 150 to 320 ° C., and further preferably 180 to 300 ° C. By setting the melting temperature within the above range, the reactivity of each of the polyester and the ketene imine compound can be increased.
  • the melt is preferably passed through a gear pump or a filter, and the melt that has passed through the filter is extruded through a die to a cooling roll and cooled and solidified.
  • the extruded melt can be brought into close contact with the cooling roll using an electrostatic application method.
  • the surface temperature of the cooling roll is preferably about 10 ° C. to 40 ° C.
  • polyester film substrate After the polyester film substrate is prepared as described above, at least one side of the polyester film substrate has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilyl group.
  • a polymer layer containing a binder having at least one functional group selected from is provided.
  • a method for forming a polymer layer in the present invention there are a method for bonding a polymer sheet having easy adhesion to a polyester film and a method by coating, but the method by coating is simple and highly uniform thin film formation. Is preferable in that it is possible.
  • the coating method is preferably performed between extrusion and heat setting, and is preferably performed at least once after this. Thereby, the adhesiveness of a film base material and a polymer layer can be improved. This is considered to have an effect that the coating component and the chemical bond are expressed by radicals generated by the cleavage of molecules on the surface of the film substrate during stretching, and adhesion can be expressed more effectively.
  • polyester film substrate it is also preferable to subject the polyester film substrate to a surface treatment prior to the application of the polymer layer, and examples thereof include corona treatment, flame treatment, ultraviolet treatment, glow treatment, and atmospheric pressure plasma treatment.
  • the polymer layer is cured by applying it in layers on a polyester film and drying prior to the stretching step.
  • the polymer layer may have a two-layer structure. In this case, it is preferable that the second layer is applied and then dried and cured.
  • the drying step is a step of supplying drying air to the polymer layer. In the drying step, it is preferable that the polymer layer is also dried and heat-treated.
  • the polyester film formed by the film forming process or the laminated film obtained by laminating the polymer layer on the polyester film can be subjected to a stretching process in the stretching process.
  • the polyester film is preferably stretched uniaxially or biaxially, and more preferably biaxially stretched.
  • Stretching in the biaxial direction includes stretching in the longitudinal direction (MD: Machine Direction) (hereinafter also referred to as “longitudinal stretching”) and stretching in the width direction (TD: Transverse Direction) (hereinafter referred to as “lateral stretching”). It is also preferred that This longitudinal stretching and lateral stretching may each be performed once, may be carried out a plurality of times, and may be simultaneously stretched longitudinally and laterally.
  • the stretching treatment is preferably performed at a glass temperature (Tg) ° C. to (Tg + 60) ° C. of the film, more preferably Tg + 3 ° C. to Tg + 40 ° C., and further preferably Tg + 5 ° C. to Tg + 30 ° C.
  • a preferred draw ratio is 280% to 500%, more preferably 300% to 480%, and still more preferably 320% to 460% on at least one side.
  • the film may be stretched evenly in the vertical and horizontal directions, but it is more preferable to stretch one of the stretch ratios more than the other and unevenly stretch. Either vertical (MD) or horizontal (TD) may be increased.
  • the biaxial stretching treatment is performed, for example, at (Tg 1 ) ° C. to (Tg 1 +60) ° C., which is the glass transition temperature of the film, once or twice in the longitudinal direction, so that the total magnification becomes 3 to 6 times.
  • the film is stretched and then applied at (Tg 1 ) ° C. to (Tg + 60) ° C. so that the magnification is 3 to 5 times in the width direction.
  • the biaxial stretching process can be stretched in the longitudinal direction using two or more pairs of nip rolls whose peripheral speed on the outlet side is increased (longitudinal stretching), and both ends of the film are gripped by chucks and orthogonally oriented (longitudinal direction). (Perpendicular direction) can be performed (lateral stretching).
  • the film in the stretching step, can be heat-treated before or after the stretching treatment, preferably after the stretching treatment.
  • heat treatment By performing heat treatment, microcrystals can be generated, and mechanical properties and durability can be improved.
  • the film may be subjected to a heat treatment at ⁇ 210 ° C. for 1 second to 60 seconds (more preferably 2 seconds to 30 seconds).
  • a thermal relaxation treatment can be performed after the heat treatment.
  • the thermal relaxation treatment is a treatment for shrinking the film by applying heat to the film for stress relaxation.
  • the thermal relaxation treatment is preferably performed in both the MD and TD directions of the film.
  • the treatment is preferably performed at a temperature lower than the heat treatment temperature, and preferably 130 ° C to 205 ° C.
  • the thermal shrinkage rate (150 ° C.) of the film is preferably 1 to 12% for MD and TD, more preferably 1 to 10%.
  • a laminated film in which the crying of the ketene compound is suppressed can be produced by the above-described method.
  • the laminated film of the present invention can be suitably used not only as a protective sheet for a solar cell module (back sheet for a solar cell module) but also for other uses.
  • the back sheet for a solar cell module of the present invention includes the above-described laminated film.
  • the laminated film of the present invention since the ketene compound produced in the polyester film is suppressed from crying on the surface of the polymer layer, even when used for a back sheet for a solar cell module, it is good as an EVA film. High adhesion can be maintained.
  • the following functional layer may be coated on the laminated film after uniaxial stretching and / or biaxial stretching.
  • a known coating technique such as a roll coating method, a knife edge coating method, a gravure coating method, or a curtain coating method can be used.
  • the back sheet for a solar cell module may further have a reflective layer (colored layer) as a functional layer.
  • the colored layer is a layer arranged in contact with the surface of the polyester film or through another layer, and can be constituted using a pigment or a binder.
  • the first function of the colored layer is to increase the power generation efficiency of the solar cell module by reflecting the light that has reached the back sheet without being used for power generation in the solar cell out of the incident light and returning it to the solar cell. is there.
  • the second function is to improve the decorativeness of the appearance when the solar cell module is viewed from the front side. In general, when a solar cell module is viewed from the front side, a back sheet can be seen around the solar cell, and the decorativeness can be improved by providing a colored layer on the back sheet.
  • the pigment examples include inorganic pigments such as titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. It is done.
  • a white pigment is preferable from the viewpoint of constituting a colored layer as a reflective layer that reflects incident sunlight.
  • titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc and the like are preferable.
  • the binder for example, polyester, polyurethane, acrylic resin, polyolefin, or the like can be used.
  • the binder is preferably an acrylic resin or a polyolefin.
  • the acrylic resin a composite resin of acrylic and silicone is also preferable.
  • preferred binders include the following.
  • polyolefins include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals).
  • the acrylic resin include Jurimer ET-410 and SEK-301 (both manufactured by Nippon Pure Chemical Industries, Ltd.).
  • Examples of the composite resin of acrylic and silicone described above include Ceranate WSA1060, WSA1070 (both manufactured by DIC Corporation), H7620, H7630, H7650 (both manufactured by Asahi Kasei Chemicals Corporation), and the like.
  • a cross-linking agent In addition to the binder and the pigment, a cross-linking agent, a surfactant, a filler, and the like may be further added to the colored layer in the present invention as necessary.
  • An undercoat layer can be provided in the laminated film of the present invention.
  • the undercoat layer may be provided between the colored layer and the polyester film.
  • the undercoat layer can be formed using a binder, a crosslinking agent, a surfactant, and the like.
  • binder contained in the undercoat layer examples include polyester, polyurethane, acrylic resin, and polyolefin.
  • epoxy, isocyanate, melamine, carbodiimide, oxazoline and other crosslinking agents, anionic and nonionic surfactants, silica and other fillers may be added to the undercoat layer.
  • the polyester film of the present invention is preferably provided with at least one of a fluorine-based resin layer and a silicon-based (Si-based) resin layer as an antifouling layer.
  • a fluorine-based resin layer or the Si-based resin layer it is possible to prevent contamination of the polyester surface and improve weather resistance.
  • it is also preferable to stick together fluorine resin films such as Tedlar (manufactured by DuPont).
  • the solar cell module of the present invention includes the polyester film of the present invention or the back sheet for the solar cell module of the present invention.
  • the solar cell module of the present invention comprises a solar cell element that converts light energy of sunlight into electric energy, a transparent substrate on which sunlight is incident, and the polyester film (back sheet for solar cell) of the present invention described above. It is arranged and arranged between.
  • the substrate and the polyester film can be formed by sealing with a resin (so-called sealing material) such as an ethylene-vinyl acetate copolymer.
  • the transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better.
  • a transparent resin such as an acrylic resin, or the like can be suitably used.
  • Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, and II Various known solar cell elements such as -VI group compound semiconductor systems can be applied.
  • the ketene imine compound represented by the general formula (1) of the present invention which was used in each Example, was a ketene imine compound having the following structure as an end-capping agent.
  • the above ketene imine compound was synthesized by the following method.
  • a ketimine compound (1) 44 g (0.1 mol), triethylbenzylammonium chloride 2 g, and chloroform 300 ml were charged into a three-necked flask, and 200 g of a 50% aqueous sodium hydroxide solution at 60 ° C. was added all at once with stirring. Stir at 50 ° C. for 1 hour. After adding 300 ml of pure water and 500 ml of chloroform to remove the aqueous layer, the solution was concentrated and washed with MEK to obtain 30 g (0.05 mol) of aziridine (1).
  • Ketimine body (4) 43 g (0.0375 mol), triethylbenzylammonium chloride 1.5 g and chloroform 230 ml were charged into a three-necked flask, and with stirring, 150 g of 50% aqueous sodium hydroxide solution at 60 ° C. was added all at once. The mixture was stirred at 40-50 ° C. for 1 hour. After adding 300 ml of pure water and 450 ml of chloroform to remove the aqueous layer, the solution was concentrated to obtain 41 g (0.0276 mol) of the aziridine compound (4).
  • ⁇ Synthesis of Aziridine Form (6) 120 g (0.227 mol) of ketimine body (6), 2.9 g of triethylbenzylammonium chloride, and 1.2 L of chloroform were charged into a three-necked flask, and 720 g of a 50% aqueous sodium hydroxide solution at 60 ° C. was added all at once while stirring. The mixture was stirred at a temperature of 40-50 ° C. for 1 hour. After adding 1.4 ml of pure water and 1.8 L of chloroform to remove the aqueous layer, the solution was concentrated to obtain 152.3 g (0.227 mol) of an aziridine compound (6).
  • the obtained oligomer was transferred to a second esterification reaction tank and reacted by stirring at a reaction tank temperature of 250 ° C. and an average residence time of 1.2 hours to obtain an oligomer having an acid value of 180 eq / ton.
  • the inside of the second esterification reaction tank is divided into three zones from the first zone to the third zone. From the second zone, an ethylene glycol solution of magnesium acetate is added, and the amount of Mg added is 75 ppm in terms of element. Then, from the third zone, an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the addition amount of P was 65 ppm in terms of element.
  • the ethylene glycol solution of trimethyl phosphate was prepared by adding a 25 ° C. trimethyl phosphate solution to a 25 ° C. ethylene glycol solution and stirring at 25 ° C. for 2 hours (phosphorus compound content in the solution: 3 .8% by mass). As a result, an esterification reaction product was obtained.
  • reaction product was transferred from the first polycondensation reaction tank to the second double condensation reaction tank. Thereafter, the reaction product was stirred in the second double condensation reaction tank at a reaction tank temperature of 276 ° C. and a reaction tank pressure of 5 torr (6.67 ⁇ 10 ⁇ 4 MPa), and the residence time was about 1.2 hours. (Transesterification reaction).
  • the reaction product obtained by the transesterification reaction is further transferred from the second double condensation reaction tank to the third triple condensation reaction tank.
  • the reaction tank internal temperature is 276 ° C. and the reaction tank internal pressure is 1.
  • the reaction (transesterification reaction) was performed under the condition of a residence time of 1.5 hours.
  • Carboxylic acid value 22 eq / ton
  • IV intrasic viscosity
  • 0.65 dl / G reaction product polyethylene terephthalate (PET)
  • the obtained PET was subjected to a heat treatment (solid phase polymerization) at 205 ° C. for 24 hours under a reduced pressure of 50 Pa using a rotary vacuum polymerization apparatus. Thereafter, nitrogen gas at 25 ° C. was allowed to flow into the vacuum polymerization apparatus, and the pellet was cooled to 25 ° C. to obtain PET having a carboxylic acid value of 15 eq / ton and IV of 0.78 dl / g.
  • the carboxylic acid value was measured by the following method.
  • the amount of terminal COOH groups was measured by a titration method. Specifically, the polyester resin was dissolved in benzyl alcohol at 205 ° C., a phenol red indicator was added, and titration was performed with a water / methanol / benzyl alcohol solution of sodium hydroxide.
  • polyester resin is charged into a hopper of a biaxial kneading and extruding machine having a diameter of 50 mm with a main feeder, a ketene imine compound is charged into a sub-feeder, and the contents are measured so that the respective contents are as shown in Table 1.
  • the resin was melted and extruded so that the maximum resin temperature reached 300 ° C.
  • the extruded melt (melt) was passed through a gear pump and a filter (pore diameter: 20 ⁇ m), and then extruded from a die to a 20 ° C. cooling roll to obtain an amorphous sheet.
  • the extruded melt was brought into close contact with the cooling roll using an electrostatic application method.
  • Examples 1 to 17 Thereafter, in Examples 1 to 17, the polymer layer coating liquid in which the binders shown in Table 1 were mixed was applied using a bar coater.
  • the composition of the coating solution for forming a polymer layer adjacent to the polyester support was as follows. -Binder 400.0 parts by mass-Nonionic surfactant 15.0 parts by mass (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content concentration 1% by mass) ⁇ Oxazoline-based crosslinking agent 180.8 parts by mass (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content concentration 25% by mass) -Distilled water 30.0 mass parts The coating liquid for polymer layer formation of the said composition was apply
  • the coating amount of the coating liquid for forming the polymer layer was adjusted so that the addition rate of the binder described in Table 1 was obtained. Then, it dried at 175 degreeC for 2 minute (s), and the polymer layer adjacent to a polyester support body was formed.
  • binders listed in Table 1 were selected and used as binders for polymer layer forming coating solutions.
  • Arrow Base SE-1013N Unitika Co., Ltd. solid concentration 20% by mass
  • Ceranate WSA1070 silicone / acrylic composite polymer manufactured by DIC Corporation, solid content concentration: 38% by mass
  • Nipol SX1105 Made by Nippon Zeon ⁇ PVA105 (polyvinyl alcohol) 50% aqueous solution Kuraray Co., Ltd.
  • PMMA ALDRICH PMMA ALDRICH
  • Comparative Example 1 a coating solution for forming a polymer layer having the following composition was prepared.
  • ⁇ PMMA manufactured by ALDRICH... 100.0 parts by mass • Distilled water... 900.0 parts by mass
  • the polymer layer forming coating solution is applied to the corona-treated surface of the polyester support so that the binder coating amount is 5.1 g / m 2 (283 parts by mass with respect to 100 parts by mass of the ketene imine compound), and at 175 ° C. for 2 minutes. Dried to form a polymer layer adjacent to a 8 ⁇ m dry thickness polyester support.
  • Comparative Examples 2 and 3 did not form a polymer layer on the polyester support.
  • the laminated film of the present invention preferably has a breaking elongation half-life of 130 hours or more and more preferably 160 hours or more before and after being subjected to a storage treatment at 120 ° C. and a relative humidity of 100%.
  • the laminated films of Examples 1 to 17 are composed of a polyester film containing the ketene imine compound represented by the general formula (1) and a polymer layer containing a binder having a specific functional group. It can be seen that the ketene compound is suppressed from crying. Thereby, the adhesiveness with the EVA film is good. In particular, Examples 2 to 4 and 6 to 16 have extremely excellent hydrolysis resistance and a suppression effect of crying out, and it can be seen that these are preferable examples.
  • Comparative Example 1 does not contain a binder having a specific functional group. Since the polyester film contains the ketene imine compound represented by the general formula (1) described above, the polyester film exhibits excellent hydrolysis resistance, but does not contain a binder having a specific functional group. Unloading is not suppressed. For this reason, adhesiveness with an EVA film is remarkably bad.
  • the polyester film contains no ketene imine compound, and no polymer layer is formed.
  • the polyester film since the polyester film does not contain a ketene imine compound, the hydrolysis resistance is extremely poor.
  • the polymer layer since the polymer layer is not formed, the adhesiveness of the polyester film and the EVA film is lowered. Since the comparative example 3 contains the ketene imine compound in the polyester film, it shows hydrolysis resistance. However, since the polymer layer is not formed, the adhesion between the polyester film and the EVA film is lowered.
  • the laminated film of the present invention can suppress the crying of the ketene compound produced in the polyester film in addition to suppressing the hydrolysis of the polyester film.
  • a ketene compound starts to cry on the surface of a polymer layer by laminating a polymer layer containing a binder having a specific functional group on a polyester film containing a ketene imine compound having a specific structure. This can be suppressed. Thereby, since the solar cell module backsheet excellent in adhesiveness with an EVA film can be obtained, industrial applicability is high.

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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)
  • Photovoltaic Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film stratifié comprenant : un film en polyester contenant un composé de céténimine qui peut être représenté par une formule générale (1) ; et une couche ou des couches polymères stratifiées directement sur l'une ou les deux surfaces du film en polyester. Le composé de cétène ne peut pas être lessivé et le film stratifié possède un degré d'adhérence élevé si la ou les couches polymères contiennent un liant qui présente au moins un groupe parmi les groupes fonctionnels suivants : un groupe carboxylique, un groupe hydroxylique, un groupe aminé, un groupe sulfonate, un groupe isocyanate, un groupe époxydique, un groupe silanol et un groupe alkoxysilyle. R1 et R2 représentent chacun un groupe aryle, un groupe aryloxy, un groupe aryl-amino-carbonyle ou un groupe aryloxycarbonyle. R3 représente un groupe alkyle ou un groupe aryle.
PCT/JP2013/084265 2012-12-20 2013-12-20 Film stratifié, feuille arrière de module de cellules solaires et module de cellules solaires Ceased WO2014098222A1 (fr)

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JP2012-278386 2012-12-20
JP2012278386A JP2014121817A (ja) 2012-12-20 2012-12-20 積層フィルム、太陽電池モジュール用バックシートおよび太陽電池モジュール

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104311496A (zh) * 2014-09-15 2015-01-28 天津师范大学 季戊四醇四三氮唑化合物及其制备方法与应用
WO2017126548A1 (fr) * 2016-01-22 2017-07-27 富士フイルム株式会社 Plaque polarisante, dispositif d'affichage d'image, et film de protection de plaque polarisante

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4094808A4 (fr) * 2020-01-24 2023-07-19 Toppan Inc. Corps d'extinction d'incendie

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692745A (en) * 1970-01-24 1972-09-19 Akzona Inc Method for chemically modifying thread-forming polyesters
JPH10130482A (ja) * 1996-10-28 1998-05-19 E I Du Pont De Nemours & Co 加水分解の安定性を改良した配向型ポリエステル製品の製造方法
WO2011093478A1 (fr) * 2010-01-27 2011-08-04 帝人株式会社 Film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692745A (en) * 1970-01-24 1972-09-19 Akzona Inc Method for chemically modifying thread-forming polyesters
JPH10130482A (ja) * 1996-10-28 1998-05-19 E I Du Pont De Nemours & Co 加水分解の安定性を改良した配向型ポリエステル製品の製造方法
WO2011093478A1 (fr) * 2010-01-27 2011-08-04 帝人株式会社 Film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104311496A (zh) * 2014-09-15 2015-01-28 天津师范大学 季戊四醇四三氮唑化合物及其制备方法与应用
CN104311496B (zh) * 2014-09-15 2016-05-18 天津师范大学 季戊四醇四三氮唑化合物及其制备方法与应用
WO2017126548A1 (fr) * 2016-01-22 2017-07-27 富士フイルム株式会社 Plaque polarisante, dispositif d'affichage d'image, et film de protection de plaque polarisante

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