JP5686691B2 - Polyester film for solar cell backside sealing material - Google Patents

Description

  The present invention has an excellent hydrolysis resistance with an ethylene vinyl acetate copolymer (hereinafter sometimes referred to as EVA), and has a polyester layer having an excellent ultraviolet resistance and hydrolysis resistance. The present invention relates to a good black polyester film for solar cell back surface sealing material and solar cell back surface sealing material.

  Photovoltaic power generation that converts light energy into electrical energy using the photoelectric conversion effect is widely performed as a means for obtaining clean energy. And with the improvement of the photoelectric conversion efficiency of a photovoltaic cell, the photovoltaic power generation system has come to be provided also in many private houses. In order to use such a solar power generation system as an actual energy source, a solar cell module having a configuration in which a plurality of solar cells are electrically connected in series is used.

The solar cell module includes a solar cell front sheet (mainly glass) / a sealing material (mainly EVA) / a photoelectric conversion layer (called a cell portion) / a sealing material (mainly EVA) / a solar cell back surface sealing material, Is a typical configuration example. As a solar cell back surface sealing material, for example, a technique using a fluorine-based film as disclosed in Patent Document 1 is disclosed. However, since the fluorine-based film is expensive, there is a problem that the price of the solar cell back surface sealing material is also expensive.
Patent Document 2 describes an invention relating to a solar cell back surface sealing material comprising a hydrolysis-resistant resin film, a metal oxide-coated resin film, and a white resin film. Since the said invention has provided the film with low hydrolysis resistance inside, a metal oxide coating resin film is required. Therefore, it is necessary to bond three films via an adhesive, which is not preferable because of high cost.

Japanese Patent Laid-Open No. 11-186575 Japanese Patent Laid-Open No. 2002-100788

  The present invention has been made in view of the above circumstances, and is excellent in hydrolysis resistance with an ethylene vinyl acetate copolymer (hereinafter sometimes referred to as EVA), and in ultraviolet resistance and hydrolysis resistance. An object of the present invention is to provide a black polyester film for a solar cell backside sealing material having an excellent polyester layer and a good partial discharge voltage, and a solar cell backside sealing material.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the above-mentioned problems can be solved by using a polyester film having a specific configuration, and have completed the present invention.

That is, the gist of the present invention is that the black pigment is contained in an amount of 0.7 to 3.0% by weight, the intrinsic viscosity (IV_A) is 0.66 dl / g or more, and the terminal carboxyl group amount (AV_A) is 26 equivalents / t. less is Poriesu Te le layer (a) and at least one of the outermost layer of the polyester film, one surface of the polyester film, a polyurethane having at least one kind of polyether backbone, crosslinking agent comprising a polymer containing an oxazoline group or a carbodiimide group A polyester film for solar cell backside sealing material, characterized in that it has a coating layer obtained by coating a coating solution containing: and the total film thickness is in the range of 250 to 350 μm.

  ADVANTAGE OF THE INVENTION According to this invention, the polyester film for solar cell backside sealing materials which has adhesiveness excellent in hydrolysis resistance with an ethylene vinyl acetate copolymer can be provided. The industrial value of the present invention is high.

The polyester film referred to in the present invention is a film stretched after cooling a molten polyester sheet extruded by a so-called extrusion method, which is melt-extruded from an extrusion die.
In the present invention, the polyester used for the polyester film refers to a polyester obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Representative polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like. Among these, polyethylene terephthalate (PET) is preferable.

  As for the amount of the compound in the polyester film of the present invention, it is necessary that titanium element and phosphorus element are detected by analysis using a fluorescent X-ray analyzer described later, and that the content of magnesium element is in a specific range.

  The titanium element content in the polyester film of the present invention is preferably 2 ppm or more. When the titanium element is less than 2 ppm, the productivity at the time of producing the polyester raw material is inferior, and the polyester raw material reaching the target degree of polymerization cannot be obtained.

  On the other hand, the upper limit of the titanium element content in the polyester film is not particularly limited, but a preferred range is 20 ppm or less, a more preferred range is 15 ppm or less, and a particularly preferred range is 9 ppm or less. When there is too much content of a titanium compound, an oligomer will be easy to byproduce in the process of melt-extruding polyester, and it will become a polyester film which the oligomer precipitated on the surface. The surface oligomer of the polyester film may cause causative substances such as contamination of the roll by causing the oligomer to be transferred to the roll used during film formation, and generation of film foreign matter.

  The phosphorus element in the polyester film of the present invention is usually derived from a phosphoric acid compound, and is added during the production of the polyester. The phosphorus element content in the polyester film of the present invention is preferably 3 ppm or more. When the phosphorus element is less than 3 ppm, the productivity at the time of production of the polyester raw material is inferior, and the polyester raw material reaching the target degree of polymerization cannot be obtained.

  On the other hand, the upper limit of the phosphorus element content in the polyester film is not particularly limited, but a preferred range is 170 ppm or less, a more preferred range is 100 ppm or less, and a particularly preferred range is 50 ppm or less. If the amount of phosphorus element is too large, gelation may occur during film formation, resulting in a foreign matter, which may cause deterioration in film quality. Examples of phosphoric acid compounds include known ones such as phosphoric acid, phosphorous acid or ester phosphonic acid compounds, phosphinic acid compounds, phosphonous acid compounds, phosphinic acid compounds, and specific examples include regular phosphoric acid. , Dimethyl phosphate, trimethyl phosphate, diethyl phosphate, triethyl phosphate, dipropyl phosphate, tripropyl phosphate, dibutyl phosphate, tributyl phosphate, diamyl phosphate, triamyl phosphate, dihexyl phosphate, tri Examples include hexyl phosphate, diphenyl phosphate, triphenyl phosphate, and ethyl acid phosphate.

  Further, it is preferable not to contain as much as possible a metal compound that can act as a catalyst in order to suppress thermal decomposition and hydrolysis, but in order to reduce the volume resistivity value at the time of melting in order to improve the productivity of the polyester film, Metals such as calcium, lithium and manganese are contained in the film. Among these, magnesium element is particularly preferable, and the magnesium element content is usually 9 to 40 ppm, preferably 10 to 30 ppm. When the elemental magnesium content is less than 9 ppm, the volume specific resistance value obtained by the method described later of the polyester film is high, and thus when the film production speed during film production is high, a sheet extruded from a die called a pinning bubble A phenomenon of poor adhesion to the casting drum is likely to occur, and it may be difficult to obtain a homogeneous film that is completely adhered and rapidly cooled. On the other hand, when the magnesium element content is 40 ppm or more, the amount of foreign matter (magnesium salt) insoluble in polyester tends to increase.

  The volume resistivity value (Ω · cm) is preferably 40 Ω · cm or less, more preferably 35 Ω · cm or less, and particularly preferably 30 Ω · cm or less. When the volume resistivity (Ω · cm) is 40 Ω · cm or more, when the film production speed is high during film production, the adhesion phenomenon between the sheet extruded from a die called a pinning bubble and the casting drum is likely to occur. It is difficult to obtain a homogeneous film that is completely tightly quenched. Although there is no particular lower limit, it is practically about 3 Ω · cm.

  The method for adding the magnesium element to the polyester film is not particularly limited. (B) a method using a polyester raw material added with a magnesium compound as a catalyst during polymerization, (b) a method using a polyester raw material with a low magnesium content, and a polyester raw material added with a magnesium compound as a catalyst during polymerization; ) A method using a polyester raw material with a low magnesium content and a polyester raw material obtained by masterbatching a magnesium compound into a polyester raw material with a low magnesium content by a kneading method, and (2) producing a film with a polyester raw material with a low magnesium content. A method of adding a magnesium compound directly from an extruder at the time of film formation is exemplified, but it is not particularly limited.

  The intrinsic viscosity (IV_A) of the polyester layer (A) is 0.66 dl / g or more, preferably 0.68 dl / g or more. Since the intrinsic viscosity of the polyester layer (A) is 0.66 dl / g or more, the strength of the polyester layer (A) is maintained even if the polyester layer (B) becomes brittle after the wet heat treatment. Later, as a whole polyester film, a film having good long-term durability and hydrolysis resistance is obtained. On the other hand, although there is no upper limit of the intrinsic viscosity of the polyester layer (A), it is about 0.90 dl / g from the viewpoint of the efficiency of the polycondensation reaction and the prevention of pressure increase in the melt extrusion process.

  The amount of terminal carboxyl groups (AV_B) of the polyester layer (A) is 26 equivalents / t or less, preferably 20 equivalents / t or less. If the amount of terminal carboxyl groups of the polyester layer (A) is 26 equivalents / t or less, the strength of the polyester layer (A) is maintained even if the polyester layer (B) becomes brittle after the wet heat treatment. Thus, a film having good long-term durability and hydrolysis resistance as a whole polyester film can be obtained. On the other hand, although there is no lower limit of the amount of terminal carboxyl groups in the polyester layer (A), it is usually about 5 equivalents / t from the viewpoints of the efficiency of the polycondensation reaction, thermal decomposition in the melt extrusion process, and the like.

  The intrinsic viscosity (IV_B) of the polyester layer (B) is 0.60 dl / g or more, preferably 0.63 dl / g or more. When the intrinsic viscosity of the polyester layer (B) is less than 0.60 dl / g, a material satisfying the adhesiveness after wet heat treatment between the polyester layer (B) and the sealing material layer cannot be obtained.

  On the other hand, although there is no upper limit of the intrinsic viscosity of the polyester layer (B), it is about 0.90 dl / g from the viewpoint of the efficiency of the polycondensation reaction and the prevention of pressure increase in the melt extrusion process.

  The terminal carboxyl group amount (AV_B) of the polyester layer (B) is 40 equivalents / t or less, preferably 35 equivalents / t or less. When the amount of terminal carboxyl groups of the polyester layer (B) is higher than 40 equivalent / t, the polyester layer (B) and the sealing material layer are not satisfactory in the adhesion after wet heat treatment. On the other hand, although there is no lower limit of the amount of terminal carboxyl groups in the polyester layer (B), it is usually about 5 equivalents / t from the viewpoints of the efficiency of the polycondensation reaction, thermal decomposition in the melt extrusion process, and the like.

  In order to improve workability in the film winding process, coating process, vapor deposition process, and the like, it is desirable that the polyester film in the present invention contains fine particles. The fine particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, lithium fluoride, aluminum oxide, and kaolin, and organic particles such as acrylic resin and guanamine resin. In addition, there can be mentioned, but not limited to, precipitated particles in which the catalyst residual is made into particles. Among these particles, porous silica particles that are aggregate particles of temporary particles are particularly preferable. Since the porous silica particles are less likely to generate voids around the film when the film is stretched, the porous silica particles have the feature of improving the transparency of the film.

  In the laminated polyester film, the fine particles are preferably contained in the outermost layer. When there is no fine particle in the outermost layer, the friction between the film and the roll is intense at the time of film formation, and scratches are easily generated on the film surface.

  The average particle diameter of primary particles constituting the porous silica particles is preferably in the range of 0.001 to 0.1 μm. If the average particle size of the primary particles is less than 0.001 μm, ultrafine particles are generated by crushing at the slurry stage, which may form aggregates and increase the number of foreign matters. On the other hand, when the average particle size of the primary particles exceeds 0.1 μm, the porosity of the particles is lost, and as a result, there is a tendency that the feature with less void generation is lost.

  Furthermore, the pore volume of the aggregated particles is in the range of 0.5) to 2.0 ml / g, preferably 0.6 to 1.8 ml / g. When the pore volume is less than 0.5 ml / g, the porosity of the particles is lost, voids are easily generated, and the transparency of the film tends to be lowered. When the pore volume is larger than 2.0 ml / g, crushing and aggregation are likely to occur, and it may be difficult to adjust the particle size.

  The method for adding particles to the polyester film in the present invention is not particularly limited, and a known method can be adopted. For example, it can be added at any stage for producing the polyester, but it is preferably added as a slurry dispersed in ethylene glycol or the like at the stage of esterification or before the start of the polycondensation reaction after completion of the transesterification reaction. The condensation reaction may proceed. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder. It is done by methods.

  The black pigment in the polyester film is one kind of black pigments such as carbon black (channel, furnace, acetylene, thermal, etc.), carbon nanotube (single wall, multilayer), aniline black, black iron oxide, etc. Two or more types can be used. Among them, it is preferable to use carbon black or black iron oxide, and it is more preferable to use carbon black.

  The content of the black pigment in the polyester layer (A) is 0.7% by weight or more, more preferably 0.8% by weight or more, and particularly preferably 0.9% by weight or more. When the black pigment content is less than 0.7% by weight, the colorability and concealment of the film are not sufficient, and the UV resistance is not satisfied. Regarding the upper limit, it is 3.0% by weight, and if it exceeds 3.0% by weight, the colorability / hiding property is saturated, and the effect of the black pigment content on the UV resistance becomes difficult to see, and the cost is reduced. It is not preferable also in terms.

  About content of the black pigment in a polyester layer (B), it is 0.7 weight% or less, Preferably it is 0.5 weight% or less, Most preferably, it is 0.3 weight% or less. When the content of the black pigment in the polyester layer (B) exceeds 0.7% by weight, the black pigment in the polyester (B) layer is already contained in the polyester layer (A). Even if the content is increased, the colorability and concealment of the polyester film as a whole are saturated, and the effect of the black pigment content on the ultraviolet resistance becomes difficult to see, and it is not preferable in terms of cost.

  In addition to the above-mentioned particles, conventionally known antioxidants, heat stabilizers, lubricants, antistatic agents, and dyes can be added to the polyester film of the present invention as necessary.

  The thickness of the polyester film of the present invention is 250 μm or more, preferably 275 μm or more. If the thickness is less than 250 μm, the partial discharge voltage does not reach 1000 V, which is not preferable as the back surface sealing material for solar cells. On the other hand, the upper limit of the thickness is 350 μm, and preferably 325 μm or less. If the thickness of the polyester film is greater than 350 μm, the unit price per area increases, which is not preferable in terms of cost.

  The thickness (D_A) of the polyester layer (A) is defined as the sum of the layers constituting the polyester layer (A). The thickness (D_B) of the polyester layer (B) is defined as the sum of the layers constituting the polyester layer (B).

  The ratio (D_B / D_A) of the thickness (D_B) of the polyester layer (B) to the thickness (D_A) of the polyester layer (A) is preferably 14 or less, more preferably 11 or less, and most preferably 9 or less. . If D_B / D_A is greater than 14, the hydrolysis resistance of the entire polyester film may not be maintained.

  In the polyester film of the present invention, improved wet heat resistance with sealing materials such as EVA and polyvinyl acetal resin (hereinafter sometimes abbreviated as PVB) which are generally used as solar cell sealing materials It is preferable to provide the coating layer to be made on the side of the polyester film in contact with EVA or PVB.

  The coating liquid component for forming the coating layer preferably contains a polyurethane having at least one of a polycarbonate skeleton or a polyether skeleton, and a crosslinking agent. The polyurethane having a polycarbonate skeleton or a polyether skeleton is obtained by using a compound having a polycarbonate skeleton or a polyether skeleton as a polyol. In addition, you may have a polycarbonate frame | skeleton and a polyether frame | skeleton simultaneously.

  The polycarbonate polyol used for the polyurethane in the coating solution component for forming the coating layer can be obtained, for example, by reaction of diphenyl carbonate, dialkyl carbonate, ethylene carbonate or phosgene with a diol. Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neo Examples include pentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane and the like. Among these, a polycarbonate polyol using 1,6-hexanediol is preferable because it is easily available industrially, is good in terms of improving adhesiveness, and has good hydrolysis resistance.

  The polycarbonate polyol has a polystyrene-equivalent number average molecular weight by gel permeation chromatography (GPC) and is preferably 300 to 5,000.

  Polyether polyols used in the coating liquid component polyurethane for forming the coating layer include polyoxyethylene polyol (polyethylene glycol, etc.), polyoxypropylene polyol (polypropylene glycol, etc.), polyoxytetramethylene polyol (polytetramethylene ether glycol, etc.) ), Copolymer polyether polyols (block copolymers and random copolymers such as polyoxyethylene glycol and polyoxypropylene glycol), and the like. Among these, polyoxytetramethylene glycol is preferable because it is excellent in terms of improving adhesiveness and also has good hydrolysis resistance.

  The polyether polyol has a number average molecular weight in terms of polyethylene glycol determined by gel permeation chromatography (GPC) and is preferably 300 to 5,000.

  The polyurethane using the above-described polycarbonate polyol or polyether polyol has better resistance to hydrolysis than the polyurethane using polyester polyol, which is another general-purpose polyol.

  Each of these polycarbonate polyols or polyether polyols may be used alone or in combination of two or more. As described above, these polycarbonate polyols and polyether polyols can be used in combination.

  Examples of the polyisocyanate used in the polyurethane as the coating solution component for forming the coating layer include known aliphatic, alicyclic, aromatic and other polyisocyanates.

  Specific examples of the aliphatic polyisocyanate include, for example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2-methylpentane- Examples include 1,5-diisocyanate and 3-methylpentane-1,5-diisocyanate.

  Specific examples of the alicyclic polyisocyanate include, for example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane-4,4′-diisocyanate, hydrogenated biphenyl-4,4′-diisocyanate, 1,4-cyclohexane diisocyanate. , Hydrogenated tolylene diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, and the like.

  Specific examples of the aromatic polyisocyanate include, for example, tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like can be mentioned.

  These polyisocyanates may be used alone or in combination of two or more.

  Examples of chain extenders include ethylene glycol, propylene glycol, butanediol, diethylene glycol, neopentyl glycol, trimethylolpropane, hydrazine, ethylenediamine, diethylenetriamine, isophoronediamine, 4,4′-diaminodiphenylmethane, 4,4 ′. -Diaminodicyclohexylmethane, water, etc.

  The polyurethane having at least one of a polycarbonate structure and a polyether structure used as a coating solution component for forming a coating layer may be one using an organic solvent as a medium, but preferably one containing water as a medium. . In order to disperse or dissolve polyurethane in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into a polyurethane resin, and a water-soluble type. In particular, a self-emulsification type in which an ionic group is introduced into the skeleton of a polyurethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance, transparency and adhesiveness of the resulting coating layer.

  As the ionic group to be introduced, examples of the anionic group include a carboxylate group, a sulfonate group, a phosphate group, and a phosphonate group, and examples of the cationic group include quaternary ammonium. For example, carboxylic acid group as an anionic group is exemplified by dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid, trimellitic acid- Ammonium salts such as bis (ethylene glycol) ester, lower amine salts, and the like can be preferably used. Moreover, about the quaternary ammonium of a cationic group, quaternization products, such as N-alkyl dialkanolamines, such as N-methyldiethanolamine and N-ethyldiethanolamine, can be used preferably. Among these ionic groups, when the carboxylate is a base and the counter ion is an organic amine having a boiling point of 150 ° C. or lower such as ammonia or triethylamine, an oxazoline-based crosslinking agent or a carbodiimide-based crosslinking agent described later It is particularly preferable in that it has a high reactivity with and increases the crosslinking density of the coating layer.

  As a method for introducing an ionic group into the urethane resin in the coating solution component for forming the coating layer, various methods can be taken in each stage of the polymerization reaction. For example, at the time of prepolymer synthesis, a resin having an ionic group can be used as a copolymerization component, or a component having an ionic group can be used as one component such as a polyol or a chain extender.

  In the coating liquid component for forming the coating layer, in addition to the above-described polyurethane, it is necessary to use a crosslinking agent together in order to impart heat resistance, heat-resistant adhesiveness, moisture resistance, and blocking resistance to the coating layer. This cross-linking agent is preferably water-soluble or water-dispersible. Specifically, in addition to melamine compounds, benzoguanamine compounds, urea compounds, acrylamide compounds, which are methylolated or alkoxymethylolated, epoxy compounds It is preferable to contain at least one selected from an isocyanate compound, a carbodiimide compound, an oxazoline compound, a silane coupling agent compound, a titanium coupling agent compound, and the like. Among these crosslinking agents, an oxazoline-based compound or a carbodiimide-based compound, which is a polymer itself, is particularly preferable because the heat and moisture resistance adhesion of the coating layer is greatly improved. Such an oxazoline-based cross-linking agent is commercially available, for example, under the trade name Epocross (registered trademark) of Nippon Shokubai Co., Ltd., and a carbodiimide-based cross-linking agent is commercially available, for example, under the trade name Carbodilite (registered trademark) of Nisshinbo Chemical Co., Ltd. . Moreover, the addition amount of these crosslinking agents is 10: 90-90: 10 by the weight ratio with respect to the polyurethane in the coating liquid component for coating layer formation, Preferably it is used in the ratio of 20: 80-80: 20. Is preferred.

  In the coating solution component for forming the coating layer, the total of the polyurethane and the crosslinking agent component described above is preferably present in an amount of 50% by weight or more, and more preferably 75% by weight or more. In addition to these resin components, other resins can be additionally added. Examples of the resin component that can be additionally added include polyester resins, acrylic resins, polyvinyl resins, and polyester polyurethane resins. However, polyester resins and polyester polyurethane resins are often poor in hydrolysis resistance, and these resins are preferably not added to the coating layer, or even if added, the added amount is preferably less than 10% by weight.

  In addition, in order to prevent blocking of the coating layer and to impart slipperiness, it is also possible to add fine particles to the coating solution component for forming the coating layer. As fine particles, for example, inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles can be used. The size of the fine particles is 150 nm or less, preferably 100 nm or less, and the addition amount in the coating layer is preferably selected in the range of 0.5 to 10% by weight.

In addition, components other than those described above can be included in the coating solution component for forming the coating layer, if necessary. For example, surfactants, antifoaming agents, coatability improvers, thickeners, antioxidants, antistatic agents, foaming agents, dyes, pigments and the like. These additives may be used alone or in combination of two or more.
The coating layer is preferably formed by coating on a polyester film as a coating solution mainly using water as a medium. The polyester film to be applied may be biaxially stretched in advance, but it is preferable to use a so-called in-line coating method in which the polyester film is stretched in at least one direction after being applied and further heat-set.

Any known method can be applied as a method of applying the coating solution to the polyester film as the substrate. Specifically, roll coating method, gravure coating method, micro gravure coating method, reverse coating method, bar coating method, roll brush method, spray coating method, air knife coating method, impregnation method, curtain coating method, die coating method, etc. It can be applied alone or in combination.
Next, a method for forming the coating layer will be described.

The coating layer in the present invention has a coating amount of 0.005 to 1.0 g as a final dry film after being dried and solidified or after being biaxially stretched or heat-set. / M ² , more preferably 0.01 to 0.5 g / m ² . In the coating amount is less than 0.005 g / m ^2, there is a tendency that adhesion becomes insufficient, when it exceeds 1.0 g / m ² is no longer the adhesive is saturated, such as blocking the reverse There is a tendency that the adverse effects of are likely to occur.

  Analysis of the components in the coating layer can be performed by surface analysis such as TOF-SIMS.

  In the present invention, the drying and curing conditions for forming the coating layer on the polyester film are not particularly limited. For example, when the coating layer is provided by off-line coating, it is usually 3 to 40 at 80 to 200 ° C. The heat treatment may be performed for 2 seconds, preferably 100 to 180 ° C. for 3 to 40 seconds.

  On the other hand, when the coating layer is provided by in-line coating, heat treatment is usually performed at 70 to 280 ° C. for 3 to 200 seconds as a guide.

  Further, irrespective of off-line coating or in-line coating, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as required. The polyester film constituting the laminated polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  In the present invention, two or more polyester melt extruders are preferably used to form a laminated film of two or more layers by a so-called coextrusion method. As the structure of the layer, an A / B structure, an A / B / A structure, or the like is conceivable using an A raw material having a high intrinsic viscosity and a B raw material having a low intrinsic viscosity.

  In the case of the A / B configuration, when the coating layer is provided, the coating layer needs to be provided at least on the B layer side, and in the case of the A / B / A configuration, the coating layer is provided on any one surface. Need to be. When the polyester film and EVA are bonded, it is necessary to contact the side with the coating layer and EVA, and when the solar cell module is assembled, the A layer needs to be the outermost layer.

  Hereinafter, although the manufacturing method of the polyester film of this invention is demonstrated concretely, as long as the summary of this invention is satisfied, this invention is not specifically limited to the following illustrations.

  That is, a dried or undried polyester chip (polyester component) by a known method is supplied to a kneading extruder and heated to a temperature equal to or higher than the melting point of the polyester component to melt. Next, the melted polyester is extruded from a die, and rapidly cooled and solidified on a rotary cooling drum so that the temperature is equal to or lower than the glass transition temperature, thereby obtaining a substantially amorphous unoriented sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum. In the present invention, an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed. Even in the melt extrusion process, the amount of terminal carboxyl groups increases depending on the conditions. Therefore, in the present invention, it is necessary to shorten the residence time of the polyester in the extruder in the extrusion process. Dry sufficiently so that the amount is 50 ppm or less, preferably 30 ppm or less. When a twin screw extruder is used, a vent port is provided, and a reduced pressure of 40 hectopascals, preferably 30 hectopascals, more preferably 20 hectopascals or less. A method such as maintaining the above is adopted.

  In the present invention, the sheet thus obtained is stretched biaxially to form a film. Specifically describing the stretching conditions, the unstretched sheet is preferably stretched 2 to 6 times at 70 to 145 ° C. in the machine direction to form a uniaxially stretched film, and then 90 to 160 ° C. in the transverse direction. Then, the film is stretched 2 to 6 times and moved to a heat setting step at 180 to 245 ° C.

  In the present invention, the polyester film can be obtained by shortening the residence time of the polyester component in the extruder in the extrusion process of the polyester chip, for example, in order to set the terminal carboxyl group amount of the polyester component in the polyester film in a specific range. . Moreover, you may obtain the polyester film whose terminal carboxyl group amount is a specific range by forming the polyester chip of low terminal carboxyl group amount into a film. In film production, if a recycled material that has undergone a melting step is blended, the amount of terminal carboxyl groups of the polyester component tends to increase outside a specific range. Therefore, it is preferable not to blend such a recycled material in the present invention. Moreover, even if it mix | blends a reproduction | regeneration raw material, it is preferable to use the flakes obtained by grind | pulverizing the film obtained by itself as it is, and about 40 weight% or less about an amount, More preferably, it is 20 weight% or less.

  In the present invention, a coating layer is formed on one side or both sides of the film in order to impart adhesiveness, antistatic property, slipperiness, releasability, etc. to the film in or after the stretching step, or corona treatment. It is also possible to perform a discharge treatment such as.

  The solar cell back surface sealing material which consists of a polyester film of this invention needs to be provided in the side which the coating layer on a polyester film adhere | attaches with EVA. If there is no coating layer, EVA and the solar cell back surface sealing material which consists of the polyester film of this invention will not adhere | attach.

  The solar cell back surface sealing material comprising the polyester film of the present invention needs to have a polyester layer (A) on the side not bonded to EVA. The side that does not adhere to EVA, that is, when assembled as a solar cell module, has the polyester layer (A) as the outermost layer, so that the solar cell back surface sealing material can irradiate sunlight directly or by reflection from the roof or the ground. When received, since the polyester layer (A) has ultraviolet resistance, deterioration due to sunlight can be prevented.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist of the present invention. In addition, the measurement and evaluation method of various physical properties of a film are shown below.

(1) Black pigment content (% by weight)
If it is a polyester raw material or a polyester film, 0.2 g is collected from a sample obtained by slicing a polyester (A) layer and a polyester (B) layer with a cutter from a polyester film, and 20 ml of phenol / tetrachloroethane = 50/50. After dissolving in the (weight ratio) mixed solution and centrifuging to precipitate only the black pigment, the supernatant is removed. The sample after removing the upper liquid is evaporated to dryness, and the weight of the sample after evaporation to dryness is measured. From the obtained measured value and 0.2 g initially weighed, the black pigment content: C (% by weight) in the polyester raw material, the polyester (A) layer and the polyester (B) layer is determined.

(2) Amount of terminal carboxyl group (equivalent / t)
If it is a polyester chip, grind it. If it is a polyester film, a polyester (A) layer and a polyester (B) layer are sliced from a polyester film with a cutter, and a sample is taken. Using a black pigment content C (% by weight) obtained above from a sample dried at 140 ° C. for 15 minutes in a hot air dryer and cooled to room temperature in a desiccator, 1 0.0 g × 100 / (100-C) was accurately weighed and collected in a test tube, 30 ml of benzyl alcohol was added, dissolved in 195 ° C. for 3 minutes while blowing dry nitrogen gas, and then 50 ml of chloroform was gradually added. In addition, it was cooled to room temperature. After only the black pigment was settled by centrifugation, the finished liquid was taken out. Add 1 to 2 drops of phenol red indicator to the supernatant, and titrate with 0.1 (N) benzyl alcohol solution of caustic soda while blowing dry nitrogen gas, and finish when the color changes from yellow to red . It is assumed that 1.0 g of the polyester raw material is contained in the supernatant. Further, as a blank, the same operation was carried out without a polyester resin sample, and the acid value was calculated by the following formula.

Acid value (equivalent / t) = (A−B) × 0.1 × f / W
[Where A is the amount of benzyl alcohol solution of 0.1N caustic soda required for titration (μl) and B is the amount of benzyl alcohol solution of 0.1N caustic soda required for titration with a blank (μl) , W is the amount (g) of the polyester resin sample, and f is the titer of the benzyl alcohol solution of 0.1N caustic soda. ]
The titer (f) of 0.1N caustic soda benzyl alcohol solution was obtained by taking 5 ml of methanol into a test tube, adding 1 to 2 drops of phenol red ethanol solution as an indicator, and 0.1N caustic soda benzyl alcohol. Titrate to the color change point with 0.4 ml of solution, then add 0.2 ml of 0.1N hydrochloric acid aqueous solution of known titer as a standard solution and add it again to the color change point with 0.1N sodium hydroxide in benzyl alcohol. Titration was performed (the above operation was performed under blowing of dry nitrogen gas).
The titer (f) was calculated by the following formula.
Titer (f) = Titer of 0.1N aqueous hydrochloric acid × Amount of collected 0.1N aqueous hydrochloric acid (μl) / Titration of 0.1N sodium hydroxide in benzyl alcohol (μl)

(3) Intrinsic viscosity (dl / g)
If it is a polyester chip, grind it. If it is a polyester film, a polyester (A) layer and a polyester (B) layer are sliced with a cutter from a polyester film, and a required quantity is extract | collected. A polyester film or a pulverized polyester raw material obtained by using the black pigment content C (% by weight) obtained above in phenol / tetrachloroethane = 50/50 (weight ratio) is 1 Add precisely weighed to 0. 0x100 / (100-C) (g / dl). After dissolving at 120 ° C. for 10 minutes, the mixture was gradually cooled to room temperature. After sedimentation of only the black pigment by centrifugation, the supernatant is taken out, the flow time of the supernatant is measured, and the flow time of the solvent alone is measured. From these time ratios, the Huggins equation is used to determine the limit. Viscosity (dl / g) was calculated. At that time, the Huggins constant was assumed to be 0.33. The concentration of the polyester raw material in the finished liquid is 1.0 (g / dl).

(4) UV resistance and UV irradiation equipment Suga Test Instruments Super Xenon Weather Meter: SX75
・ Ultraviolet irradiation device conditions Irradiance: 180 W / m ² (in the range of 300-400 nm)
Filter: Inner / Outer = Quartz / # 275
Black panel temperature: spraying / non-spraying = non-control / 63 ° C
Test bath temperature: spraying / non-spraying = 28 ° C./non-control Test bath humidity: spraying / non-spraying = 95% RH / 50% RH
Cycle time: spraying / non-spraying = 18 minutes / 102 minutes Evaluation method Super xenon weather meter: Using SX75 (manufactured by Suga Test Instruments), the above-mentioned conditions for the surface of the polyester film with the polyester layer (A) Process with. With Autograph AG-I (manufactured by Shimadzu Corporation), the tensile elongation at break was measured as the mechanical properties of the film at a speed of 200 mm / min with respect to the film forming direction (MD). Measure and obtain the tensile elongation at break rate. The tensile breaking elongation retention rate is obtained from the following formula, that is, the quotient of the tensile breaking elongation before and after ultraviolet irradiation.

Tensile elongation at break [%] = “tensile elongation at break after super xenon weather meter treatment” ÷ “tensile elongation at break before super xenon weather meter treatment” × 100
From the time when the tensile elongation at break maintenance rate reached less than 10%, the following criteria were used for evaluation.
◯: Time at which the tensile fracture elongation maintenance ratio reached less than 10%: 500 hr or more Δ: Time at which the tensile fracture elongation maintenance ratio reached less than 10%: 200 hr or more and less than 500 hr ×: Tensile fracture elongation maintenance ratio of 10 Time to reach less than%: less than 200 hr

(5) Hydrolysis resistance test Using a personal pressure cooker (manufactured by Hirayama Seisakusho Co., Ltd.), the polyester film is treated in an atmosphere of 120 ° C.-100% RH. With Autograph AG-I (manufactured by Shimadzu Corporation), the tensile elongation at break was measured as the mechanical properties of the film at a speed of 200 mm / min with respect to the film forming direction (MD). Measure and obtain the tensile elongation at break rate. The tensile breaking elongation maintenance ratio is obtained from the following formula, that is, the quotient of the tensile breaking elongation before and after the personal pressure cooker treatment.

Tensile rupture elongation retention rate [%] = “tensile rupture elongation after personal pressure cooker treatment” ÷ “tensile rupture elongation before personal pressure cooker treatment” × 100
From the time when the tensile elongation at break maintenance rate reached less than 10%, the following criteria were used for evaluation.
A: Time at which the tensile fracture elongation maintenance ratio reached less than 10%: 78 hr or more O: Time at which the tensile fracture elongation maintenance ratio reached less than 10%: 72 hr or more and less than 78 hr Δ: Tensile fracture elongation maintenance ratio of 10 Time when it reached less than%: 66 hr or more and less than 72 hr ×: Time when the tensile fracture elongation retention rate reached less than 10%: less than 66 hr

(6) EVA easy adhesion Two small pieces of polyester film having a length of 300 mm and a width of 25 mm were cut out so that the longitudinal direction was MD. On the other hand, one piece of the EVA film having a length of 50 mm and a width of 25 mm was cut out and stacked so that the EVA film was sandwiched between the application layer surfaces of the two pieces of the polyester film. This was laminated using a heat seal device (TP-701-B manufactured by Tester Sangyo Co., Ltd.). The EVA film used was 485.00 (standard curing type, thickness 0.5 mm) manufactured by Etimex, Germany, and the heat seal conditions were a temperature of 150 ° C. and a pressure of 0.13 MPa for 20 minutes. In order to measure the adhesive strength with EVA, first, a sample having a length of 300 mm and a width of 15 mm is cut out from a polyester film / EVA film laminate piece having a width of 25 mm. The non-laminated end of this 15 mm wide polyester film piece is mounted in a tensile / bending tester (EZGraph manufactured by Shimadzu Corporation). Subsequently, the force (adhesive strength) required to separate the polyester film / EVA film laminate at an angle of 180 ° and a speed of 100 mm / min was measured for 10 samples, and the average values were classified as follows. did.
◎: Adhesive strength is 50 N / 15 mm width or more ○: Adhesive strength is 30 N / 15 mm width to less than 50 N / 15 mm width Δ: Adhesive strength is 10 N / 15 mm width to less than 30 N / 15 mm width ×: Adhesive strength is less than 10 N / 15 mm width

(7) Moisture and heat resistant EVA easy adhesion Using a 25 mm wide test piece of polyester film / EVA film laminate prepared as described above, a personal pressure cooker apparatus (manufactured by Hirayama Seisakusho Co., Ltd.) is used to make the polyester film 120 ° C.-100. The film was wet heat treated for 48 hours in an atmosphere of% RH. Next, after adjusting the temperature and humidity at 23 ° C. × 50% RH for 24 hours, a measurement sample having a width of 15 mm is cut out from the sample, and the force (adhesion) required for separating the polyester film / EVA film laminate is cut in the same manner as described above. The average value of (strength) was determined.
From this value and the adhesive strength before the wet heat treatment, the adhesive strength retention was calculated by the following formula and judged according to the following criteria.
Adhesive strength retention rate (%) = (Adhesive strength after wet heat treatment) / (Adhesive strength before wet heat treatment)
A: Retention ratio is 70% or more B: Retention ratio is less than 50-70% B: Retention ratio is less than 30-50% P: Retention is less than 30%, and peeling due to cohesive failure of the polyester layer is observed XC: Retention rate of less than 30%, interfacial peeling of polyester / coat layer or EVA layer / coat layer is observed

(8) Partial discharge voltage Based on the European safety standard EN50178, the partial discharge voltage was measured with KIKUSUI KPD2050. Evaluation is based on the following criteria.
○: 1000V or more ×: less than 1000V

Next, the polyester raw material used in the following examples will be described.
<Method for producing polyester (1)>
Continuous polymerization apparatus comprising one slurry preparation tank, a two-stage esterification reaction tank connected in series thereto, and a three-stage melt polycondensation tank connected in series to the second esterification reaction tank And terephthalic acid and ethylene glycol are continuously fed to the slurry preparation tank at a weight ratio of 100: 45, and an ethylene glycol solution of ethyl acid phosphate is contained as a phosphorus atom in the produced polyester resin. A slurry is prepared by continuously adding, stirring and mixing in an amount of 4 ppm by weight, and this slurry is set at 267 ° C., a relative pressure of 100 kPa, and an average residence time of 4 hours under a nitrogen atmosphere. The first stage esterification reaction tank containing the reaction product is continuously fed at a flow rate of 120 kg / hr, and then the first stage ester The reaction product, 265 ° C. under a nitrogen atmosphere, the relative pressure 5 kPa, and continuously transferred to the second stage esterification reaction tank set for an average residence time of 2 hours, was further esterification reaction. At that time, an amount of 322 mol / ton was continuously supplied to the polyester resin producing ethylene glycol through the upper pipe provided in the second stage esterification reaction tank. In this case, the esterification rate in the second stage esterification reaction tank was 97%.

The above esterification reaction product was continuously supplied to the first stage polycondensation reaction tank via the transfer pipe. At this time, the discharge pressure of the transfer pump provided in the transfer pipe was 500 kPa. A 0.6 wt% solution of magnesium acetate tetrahydrate in ethylene glycol is continuously added to the esterification reaction product in the transfer pipe in such an amount that the content as magnesium atoms is 7 ppm by weight with respect to the produced polyester resin. Added to. Using an addition pipe, an ethylene glycol solution of tetra-n-butyl titanate was continuously added to the resulting polyester resin in an amount such that the content as titanium atoms was 4 ppm by weight.

  The melt polycondensation reaction conditions were 269 ° C. in the first stage polycondensation reaction tank, absolute pressure 4 kPa, average residence time 1 hour, 274 ° C. in the second stage polycondensation reaction tank, 0.4 kPa absolute pressure, average residence time The time was 0.9 hours, the third stage polycondensation reaction tank was 277 ° C., the absolute pressure was 0.2 kPa, and the average residence time was 1 hour. The melt polycondensation reaction product taken out from the third stage polycondensation reaction tank is extruded from a die into a strand, cooled and solidified, cut with a cutter, and one piece of polyester resin chip having an average particle weight of 24 mg: polyester (1). Polyester (1) had an intrinsic viscosity of 0.64 (dl / g) and a terminal carboxyl group content of 14 (equivalent / t).

<Method for producing polyester (2)>
Polyester (1) is used as a starting material, and continuously fed in a stirrer crystallizer maintained at about 160 ° C. in a nitrogen atmosphere with the chips not overlapping so that the residence time is about 60 minutes. After being crystallized, it is continuously supplied to a tower-type solid phase polycondensation device, and the residence time is 215 ° C. under a nitrogen atmosphere so that the intrinsic viscosity of the resulting polyester resin is 0.83 (dl / g). Was adjusted for solid phase polycondensation to obtain polyester (2). The amount of terminal carboxyl groups was 6 (equivalent / t).

<Method for producing polyester (3)>
100 parts by weight of dimethyl terephthalate and 200 parts by weight of ethylene glycol are used as starting materials, and as a transesterification catalyst, the magnesium content per 1 t of polyester resin from which magnesium acetate tetrahydrate can be obtained is 46 g / resin t. In addition, the reaction start temperature was 150 ° C., and the reaction temperature was gradually increased as methanol was distilled off. After 4 hours, the transesterification reaction was substantially terminated.
This reaction mixture was transferred to a polycondensation tank, and an ethylene glycol slurry solution consisting of a mixture of silica particles having an average particle diameter of 2.5 μm, ethyl acid phosphate, magnesium acetate tetrahydrate, and tetra-n-butyl titanate was added. The polycondensation reaction was performed for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg.

  The amount of each compound in the ethylene glycol slurry solution is 74 g / resin t as the phosphorus element amount for ethyl acid phosphate so that the silica particles are 3.0% by weight with respect to the content of the obtained polyester. Thus, for magnesium acetate tetrahydrate, the amount of magnesium element is 46 g / resin t (including the magnesium added at the time of transesterification, the total amount of magnesium element is 92 g / resin t). -N-Butyl titanate is adjusted so that the amount of titanium element is 5 g / resin t.

  After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.60 due to a change in stirring power in the reaction tank, and the polymer was discharged under nitrogen pressure to obtain polyester (3). The intrinsic viscosity was 0.60 (dl / g), and the terminal carboxyl group content was 21 (equivalent / t).

<Method for producing polyester (4)>
100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol are used as starting materials, and tetra-n-butyl titanate is obtained as a catalyst. The amount of titanium atoms per 1 ton of polyester resin is 5 g / resin t. In the reactor, the reaction start temperature was 150 ° C., and the reaction temperature was gradually increased as methanol was distilled off. After 4 hours, the transesterification reaction was substantially terminated. This reaction mixture was transferred to a polycondensation tank and subjected to a polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.55 (dl / g) due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure to obtain a polyester (4) chip. . The intrinsic viscosity was 0.55 (dl / g), and the terminal carboxyl group content was 35 (equivalent / t).

<Method for producing polyester (5)>
Polyester chip (4) was solid-phase polymerized at 220 ° C. under vacuum to obtain polyester (5). The intrinsic viscosity was 0.75 (dl / g), and the terminal carboxyl group content was 25 (equivalent / t).

<Method for producing polyester (6)>
Starting from 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.02 part of magnesium acetate tetrahydrate as a catalyst is added to the reactor, the reaction start temperature is set to 150 ° C., and the methanol is gradually distilled off. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After adding 0.03 part of ethyl acid phosphate to this reaction mixture, it moved to the polycondensation tank, added 0.04 part of antimony trioxide, and performed polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.64 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure to obtain a polyester (6) chip. This polyester had an intrinsic viscosity of 0.64 (dl / g) and a terminal carboxyl group content of 45 (equivalent / t).

<Production method of polyester (7): black MB>
The polyester (2) is subjected to a twin screw extruder with a vent, and carbon black (oil furnace black average primary particle size 30 nm) is supplied so as to be 20% by weight to form a chip. Black master batch pellets were obtained. The obtained pellet had a carbon black concentration C of 20% by weight, the amount of terminal carboxyl groups of the polyester component corrected with the carbon black concentration C was 51 (equivalent / t), and the intrinsic viscosity was 0.63 (dl / g). .

<Production method of polyester (8): production reference example>
In the production method of polyester (1), an attempt was made to produce a polyester by the same method except that ethyl acid phosphate was not added. At that time, the esterification rate was not increased, the polycondensation activity was low, the intrinsic viscosity of the obtained polyester resin was not increased, and the polyester was not suitable for film use.

<Production method of polyester (9): production reference example>
In the production method of polyester (1), an attempt was made to produce polyester by the same method except that tetra-n-butyl titanate was not added. At that time, the intrinsic viscosity did not increase, and the polyester was not suitable for film use.

Examples of compounds constituting the coating layer are as follows.
(Example compounds)
-Urethane U1: Polyurethane water dispersion which is polyurethane (counter ion of carboxylic acid is ammonia) composed of polytetramethylene glycol having a number average molecular weight of about 1000, dimethylolpropionic acid and isophorone diisocyanate U2: polycarbonate polyol of hexamethylenediol (number Aqueous dispersion of polyurethane (average counter weight of triethylamine) consisting of dimethylolpropionic acid and hydrogenated diphenylmethane-4,4'-diisocyanate (average molecular weight about 1000) U3: polyester of aromatic polyester and aliphatic diisocyanate DIC Corporation trade name Hydran (registered trademark) AP-40F, which is an aqueous polyurethane dispersion.

Polyester E1: DIC Corporation trade name Finetech (registered trademark) ES-670, which is an aqueous dispersion of an aromatic polyester
・ Oxazoline X1: Oxazoline-based water-soluble resin cross-linking agent Nippon Shokubai Co., Ltd. Brand name Epocross (registered trademark) WS-500
X2: Carbodiimide water-soluble resin crosslinking agent Nisshinbo Chemical Co., Ltd. Trade name Carbodilite (registered trademark) V-02-L2
X3: Water-soluble epoxy-based cross-linking agent Nagase ChemteX Corporation Brand name Denacol (registered trademark) EX-521
Silica D1: Silica fine particle aqueous dispersion (average particle diameter 60 nm)

(Example of coating solution)
A coating solution for the coating layer was prepared as shown in Table 1 below.

Example 1:
A polyester mixture obtained by mixing the polyester (2), polyester (3) and polyester (7) at a ratio of 91: 4: 5 was charged into a vented twin-screw extruder (A). The inner diameter D_A of the vented twin-screw extruder (A) was 140 mm, the discharge amount Q_A was 1500 kg / hr, the screw rotation speed N_A was 120 rpm, and the pressure reduction degree of the vent hole was 5 mmHg. The raw material is melt-kneaded at 290 ° C. in a twin-screw extruder, and the obtained melt is extruded into a slit shape. An unstretched single layer sheet was obtained by quenching and solidifying on a casting drum whose surface temperature was set to 40 ° C. using an electrostatic application adhesion method. The obtained sheet was stretched 3.3 times in the longitudinal direction at 89 ° C., and then the coating solution 1 shown in Table 1 was applied to the lower surface of the longitudinally stretched film to preheat / laterally stretch / heat fix 1 / heat fix 2 / Film formation was performed by introducing the temperature [° C.] in each zone of heat setting 3 / cooling to 115/135/180/225/180/125 ° C. A 300 μm thick polyester film having a coating amount (after drying) of 0.03 g / m ² was obtained. The properties and evaluation results of the obtained film are shown in Table 2 below.

Examples 2-6:
In Example 1, the polyester raw material in the mixture and the operating conditions were changed to the contents shown in Table 2, and the same method as in Example 1 except that the film forming speed was changed to adjust the thickness as necessary. A film was obtained. The properties and evaluation results of the obtained film are shown in Table 2.

Example 7:
A polyester mixture prepared by mixing the polyester (1), the polyester (2) and the polyester (3) at a ratio of 90: 6: 4 is put into a vented twin-screw extruder (B), and the polyester (2), A polyester mixture obtained by mixing polyester (3) and polyester (7) at a ratio of 91: 4: 5 was charged into a twin screw extruder (A) with a vent. The inner diameter D_B of the vented twin screw extruder (B) is 140 mm, the discharge amount Q_B is 1500 kg / hr, the screw rotation speed N_B is 120 rpm, the degree of vacuum of the vent hole is 5 mmHg, and the vented twin screw extruder (A) The inner diameter D_A was 90 mm, the discharge amount Q_A was 300 kg / hr, the screw rotation speed N_A was 67 rpm, and the pressure reduction degree of the vent hole was 5 mmHg.
Both raw materials are melt-kneaded in a twin-screw extruder at 290 ° C., and the resulting melt is merged in a multilayer T die so as to have a composition ratio of A / B = 5/1 and extruded into a slit shape. . Using an electrostatic application adhesion method, the sheet was rapidly cooled and solidified on a casting drum set to a surface temperature of 40 ° C. to obtain a laminated sheet composed of two types of unstretched two layers. The obtained sheet was stretched 3.3 times in the longitudinal direction at 89 ° C., and then the coating liquid 1 shown in Table 2 was applied to the lower surface of the longitudinally stretched film to preheat / laterally stretch / heat fix 1 / heat fix 2 / Film formation was performed by introducing the temperature [° C.] in each zone of heat setting 3 / cooling to 115/135/180/225/180/125 ° C. A 300 μm thick polyester film having a coating amount (after drying) of 0.03 g / m ² was obtained. The thickness (μm) of the polyester (A) layer / polyester (B) layer was 250/50. The properties and evaluation results of the obtained film are shown in Table 3 below.

Examples 8-26:
In Example 7, the polyester raw material in the mixture and the operating conditions were changed to the contents shown in Tables 3 to 7, and the same as in Example 7 except that the film forming speed was changed for thickness adjustment as necessary. The film was obtained by the method. The characteristic and evaluation result of the obtained film are shown in Tables 3-7.

Example 27:
In Example 7, the polyester raw material in the mixture and the operating conditions were changed to the contents shown in Table 8 below, and the same as in Example 7 except that the film forming speed was changed for thickness adjustment as necessary. A film was obtained by the method. The properties and evaluation results of the obtained film were good as shown in Table 8, but the effect corresponding to the amount of black pigment added in the polyester layer (B) was not obtained with respect to UV resistance.

Example 28:
A polyester mixture prepared by mixing the polyester (1), the polyester (2) and the polyester (3) at a ratio of 90: 6: 4 is put into a vented twin-screw extruder (B), and the polyester (2), A polyester mixture obtained by mixing polyester (3) and polyester (7) in a ratio of 91: 4: 1 was put into a twin screw extruder (A) with a vent. The inner diameter D_B of the vented twin screw extruder (B) is 140 mm, the discharge amount Q_B is 1500 kg / hr, the screw rotation speed N_B is 120 rpm, the degree of vacuum of the vent hole is 5 mmHg, and the vented twin screw extruder (A) The inner diameter D_A was 90 mm, the discharge amount Q_A was 300 kg / hr, the screw rotation speed N_A was 67 rpm, and the pressure reduction degree of the vent hole was 5 mmHg. Both raw materials are melt-kneaded in a twin-screw extruder at 290 ° C., and the resulting melt is merged in a multilayer T die so that the composition ratio is A / B / A = 1/10/1. Extrude into a shape. Using an electrostatic application adhesion method, the sheet was rapidly cooled and solidified on a casting drum set to a surface temperature of 40 ° C. to obtain a laminated sheet composed of two types of unstretched two layers. The obtained sheet was stretched 3.3 times in the longitudinal direction at 89 ° C., and then the coating liquid 1 shown in Table 2 was applied to the lower surface of the longitudinally stretched film to preheat / laterally stretch / heat fix 1 / heat fix 2 / Film formation was performed by introducing the temperature [° C.] in each zone of heat setting 3 / cooling to 115/135/180/225/180/125 ° C. A polyester film having a thickness of 300 (μm) having a coating amount (after drying) of 0.03 g / m ² was obtained. The thickness (μm) of the polyester (A) / polyester (B) layer / polyester (A) layer was 25/250/25. The characteristics and evaluation results of the obtained film are shown in Table 8 below.

Comparative Examples 1-4:
In Example 7, the polyester raw material in the mixture and the operating conditions were changed to the contents shown in Table 9 below, and the same as in Example 7 except that the film forming speed was changed for thickness adjustment as necessary. A film was obtained by the method. The properties and evaluation results of the obtained film are shown in Table 9 below.

Comparative Example 5:
In Example 7, the polyester raw material in the mixture and the operating conditions were changed to the contents shown in Table 9, and the same method as in Example 7 except that the film forming speed was changed to adjust the thickness as necessary. A film was obtained. The properties and evaluation results of the obtained film were good, but the physical properties of UV resistance were saturated with respect to the amount of black MB introduced.

  The polyester film of the present invention can be suitably used as, for example, a solar cell back surface sealing material.

Claims (4)

The black pigment containing 0.7 to 3.0 wt%, and the intrinsic viscosity (IV_A) is 0.66 dl / g or more, the amount of terminal carboxyl groups (AV_A) is 26 eq / t or less is Poriesu Te le layer ( A) is at least one of the outermost layers of the polyester film, and a coating solution containing a polyurethane having at least one polyether skeleton and a crosslinking agent made of a polymer containing an oxazoline group or a carbodiimide group is applied to one side of the polyester film. The polyester film for solar cell backside sealing materials which has the coating layer obtained by this, and the whole film thickness is the range of 250-350 micrometers. The black pigment containing 0.7 wt% or less, an intrinsic viscosity (IV_B) is at 0.60 dl / g or more, the amount of terminal carboxyl groups (AV_B) is Poriesu Te le layer is not more than 40 eq / t (B) is The polyester film for solar cell backside sealing material according to claim 1, wherein the polyester film has at least one layer, and the ratio (D_B / D_A) of the thickness D_B of the polyester layer (B) to the thickness of the polyester layer (A) is 14 or less. Polyurethane in the coating solution, polytetramethylene glycol and dimethylolpropionic acid and isophorone diisocyanate polyurethane (counter ion of the carboxylic acid ammonium) der Ru請 Motomeko 1 or a rear surface of a solar cell sealing material according to 2 Polyester film. It has an ethylene vinyl acetate copolymer (EVA) layer on the coating layer of the film in any one of Claims 1-3, and the polyester film surface on the opposite side of the said EVA layer is comprised from a polyester layer (A). The solar cell back surface sealing material characterized by the above-mentioned.