WO2013015041A1 - ポリエステルフィルムの製造方法、ポリエステルフィルム、太陽電池用バックシート、及び太陽電池モジュール - Google Patents
ポリエステルフィルムの製造方法、ポリエステルフィルム、太陽電池用バックシート、及び太陽電池モジュール Download PDFInfo
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- WO2013015041A1 WO2013015041A1 PCT/JP2012/065511 JP2012065511W WO2013015041A1 WO 2013015041 A1 WO2013015041 A1 WO 2013015041A1 JP 2012065511 W JP2012065511 W JP 2012065511W WO 2013015041 A1 WO2013015041 A1 WO 2013015041A1
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- Prior art keywords
- polyester
- resin
- laminated
- molten resin
- film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
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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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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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
- B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
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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
- B32B2457/00—Electrical equipment
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- 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 method for producing a polyester film, a polyester film, a solar cell backsheet, and a solar cell module.
- polyester In recent years, a resin material such as polyester has been used for the back sheet disposed on the side opposite to the sunlight incident side of the solar cell module. Polyester usually has many carboxyl groups and hydroxyl groups on its surface, and tends to undergo hydrolysis in an environment where moisture exists, and tends to deteriorate over time. For this reason, polyesters used in solar cell modules and the like that are constantly exposed to wind and rain, such as outdoors, are required to have reduced hydrolyzability.
- the viscosity increases as the degree of polymerization increases, the stretching stress increases, and the processing becomes difficult.
- a high-viscosity polyester resin is not suitable for film formation.
- the method using the end-capping material there is a concern that although the increase in melt viscosity is small, foreign matters are generated due to gelation and the surface shape is roughened.
- a polyester film is produced using a polyester recycling raw material for the purpose of cost reduction or the like (for example, see Japanese Patent Application Laid-Open No. 7-323511), the above-mentioned concern becomes remarkable.
- polyester raw material resin A composed of polyester raw resin A1 and A2 having an IV of 0.60 to 0.85 and an AV of 5 to 20 equivalent / ton, and an IV of 0.55 to 0.80.
- a polyester resin recycled material B having an AV of 35 equivalents / ton or less is prepared, and each of the raw material resin A1 and the mixed raw material resin including the resin A2 and the recycled material B (10 to 40% by mass) has a water content of 100 ppm or less. And dried so that the temperature of the molten resin extruded from the T die is 280 to 300 ° C., and the thickness of the second molten resin film made of the resin A1 is made of the resin A2 and the recycled material B.
- the laminated polymer film is cooled and solidified on a cast roll in a state of being laminated so as to be thicker than the film of the first molten resin, and after forming a laminate composed of at least two layers, a biaxial stretching is performed.
- METHOD FOR PRODUCING ester film, and the laminated polyester film prepared in the process, the back sheet for a solar cell having a laminated polyester film, and the solar cell module having a back sheet for the solar cell is provided.
- the present invention relates to a method for producing a laminated polyester film capable of producing a laminated polyester film excellent in hydrolysis resistance while suppressing the occurrence of uneven thickness and an increase in production cost, as well as excellent hydrolysis resistance and uneven thickness.
- the main object is to provide a laminated polyester film in which is suppressed.
- Polyester raw material resin A comprising polyester raw resin A1 and A2 having an intrinsic viscosity of 0.60 to 0.85 and a carboxyl group amount of 5 to 20 equivalents / ton, and an intrinsic viscosity of 0.55 to
- a first molten resin obtained by melting the polyester raw material resin A1 dried in the first drying step and a second molten resin obtained by melting the mixed raw material resin dried in the second drying step are shared.
- the first molten resin and the second molten resin that have been melt-extruded have a thickness of the second molten resin larger than that of the first molten resin, and the first molten resin.
- a method for producing a laminated polyester film having ⁇ 2> The method for producing a laminated polyester film according to ⁇ 1>, wherein at least one of the polyester raw material resin A and the recycled material B is a polyester resin synthesized using a titanium compound as a polymerization catalyst.
- the titanium compound includes an organic chelate titanium complex having at least one organic acid as a ligand.
- ⁇ 4> In the melt extrusion step, at least one terminal blocker selected from an epoxy compound or a carbodiimide compound is added to at least one of the first molten resin and the second molten resin with respect to the total mass of the laminated polyester film.
- ⁇ 5> In the molding step, the melted and extruded second molten resin film is cooled and solidified on a cast roll in a laminated state in which the melted and extruded first molten resin film is sandwiched between three layers.
- the manufacturing method of the laminated polyester film as described in 2.
- the intrinsic viscosity is 0.55 or more and the carboxyl group amount is 30 equivalents / ton or less, which is produced by the method for producing a polyester film according to any one of ⁇ 1> to ⁇ 6>.
- a solar cell module comprising the solar cell backsheet described in ⁇ 9>.
- a method for producing a laminated polyester film that can produce a laminated polyester film excellent in hydrolysis resistance while suppressing occurrence of thickness unevenness and an increase in production cost, and excellent in hydrolysis resistance.
- a laminated polyester film in which thickness unevenness is suppressed is provided.
- the present inventor believes that even if the intrinsic viscosity difference of each layer is large, it is possible to control the thickness of each layer by providing a temperature difference with an extruder of each layer so that the melt viscosity is as close as possible at the time of melt extrusion of each layer. It was. However, when the extrusion temperature is increased and the molten resin temperature is increased in order to lower the melt viscosity of the raw material resin having a high intrinsic viscosity, the raw material resin is decomposed to increase the amount of carboxyl groups, resulting in a decrease in hydrolysis resistance.
- the raw material resin A has a cylindrical shape or sphere with a diameter of 3 mm or more, called a pellet, and a cubic shape with a length of 3 mm or more. Because melted parts coexist, a difference in melt viscosity occurs.
- shearing force is generated by a screw in the extruder, shearing heat is generated, the temperature of the molten resin is increased, pyrolysis is performed, the amount of carboxyl groups is increased, and hydrolysis resistance is decreased.
- the recycled material B has a thickness of 2 mm or less on the flakes obtained by pulverizing the film, and is easier to melt than the pellet.
- the difference in melt viscosity in the extruder can be reduced by the blending ratio. As a result, the amount of heat generated by shearing can be reduced, the rise in molten resin temperature is also small, and thermal decomposition can be suppressed.
- the present inventor when producing a laminated polyester film excellent in hydrolysis resistance, raises the intrinsic viscosity of the raw material resin constituting each layer overall, and the thickness is the largest,
- the raw material resin of the layer (core layer) where the supply of the raw material resin becomes large is mixed with a recycled material having a relatively low intrinsic viscosity, and the shear heat generation is kept lower than the thin layer (skin layer) laminated on the core layer,
- the melt viscosity can be measured based on JIS K7210 or K7390 Annex 2.
- the method for producing the laminated polyester film of the present invention comprises: Polyester raw material resins A1 and A2 having an intrinsic viscosity of 0.60 to 0.85 and a carboxyl group amount of 5 to 20 equivalents / ton, an intrinsic viscosity of 0.55 to 0.80, and a carboxyl group amount of A raw material preparation step of preparing a recycled material B of a polyester resin that is 35 equivalents / ton or less; A first drying step of drying the polyester raw resin A1 to a water content of 100 ppm or less; Second drying for drying the mixed raw material resin containing the polyester raw material resin A2 and the recycled material B, wherein the ratio of the recycled material B to the total weight of the polyester resin is 10 to 40% by mass to a water content of 100 ppm or less Process, A first molten resin obtained by melting the polyester raw material resin A1 dried in the first drying step and a second molten resin obtained by melting the mixed raw material resin dried in the second drying step are shared.
- the first molten resin and the second molten resin that have been melt-extruded have a thickness of the second molten resin larger than that of the first molten resin, and the first molten resin.
- polyester raw material resins A1 and A2 having an intrinsic viscosity of 0.60 to 0.85 and a carboxyl group amount of 5 to 20 equivalents / ton, an intrinsic viscosity of 0.55 to 0.80, and a carboxyl group A recycled material B of a polyester resin having an amount of 35 equivalents / ton or less is prepared.
- the polyester raw resin A1 is used to form a thin layer (sometimes referred to as a “skin layer”) that is the outermost surface layer of the laminated polyester film to be manufactured.
- the polyester raw resin A2 and the recycled material B are The layer is thicker than the skin layer and is used to form a layer (sometimes referred to as a “core layer”) that becomes a base material of the laminated polyester film.
- Polyester resins having an intrinsic viscosity (IV) of 0.60 to 0.85 and a carboxyl group content (AV) of 5 to 20 equivalents / ton are prepared as the polyester raw resin A1 and A2.
- the raw materials resins A1 and A2 may be the same material or different materials as long as the intrinsic viscosity (IV) is 0.60 to 0.85 and the carboxyl group amount (AV) is 5 to 20 equivalents / ton.
- the polyester raw resin A1 and A2 may be collectively referred to as “polyester raw resin A”.
- the IV of the raw material resin can be adjusted by the polymerization method and polymerization conditions. Specifically, when solid phase polymerization is performed after liquid phase polymerization, a polyester resin having an intrinsic viscosity IV of 0.60 to 0.85 can be obtained by adjusting the processing temperature, processing time, processing atmosphere moisture, and oxygen concentration. it can. In the melt extrusion process of the polyester resin, heat is easily generated by shearing, and the amount of carboxyl groups is likely to increase by thermal decomposition. However, if a polyester resin having an IV of 0.60 to 0.85 is used, the raw resin is It can be melted without causing excessive shearing heat by sufficiently kneading, and the increase in the amount of carboxyl groups can be effectively suppressed.
- the polyester raw material resin A preferably has an intrinsic viscosity (IV) of 0.60 to 0.80, and more preferably 0.70 to 0.80.
- the AV of the polyester raw material resin A can be adjusted by the polymerization method and polymerization conditions. Specifically, when performing solid phase polymerization after liquid phase polymerization, a polyester resin having a carboxyl group amount (AV) of 5 to 20 equivalents / ton is obtained by adjusting processing temperature, processing time, processing atmosphere moisture, and oxygen concentration. be able to.
- AV carboxyl group amount
- the AV of the polyester raw material resin A is less than 5 equivalents / ton, the linearity of the molecular chain is increased and crystallization is facilitated, the shear heating value during melting is increased, the AV value is increased, and the intrinsic viscosity is decreased. When it exceeds an equivalent / ton, hydrolysis resistance will fall.
- the amount of carboxyl groups in the polyester raw material resin A is preferably 5 to 15 equivalents / ton, and more preferably 8 to 15 equivalents / ton.
- “equivalent / ton (eq / t)” represents a molar equivalent per ton.
- the melting point Tm of the polyester raw material resin A is preferably in the range of 250 ° C. to 265 ° C., and more preferably in the range of 255 ° C. to 260 ° C.
- the melting point Tm is a value determined by differential scanning calorimetry at a heating rate of 5 to 20 ° C./min.
- the polyester resin A can be obtained by polycondensing a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing ethylene glycol as a main component.
- a titanium (Ti) compound is used as a catalyst, and the amount of Ti added is 1 ppm or more and 30 ppm or less, more preferably 2 ppm or more and 20 ppm or less, more preferably 3 ppm or more and 15 ppm, in terms of element. Polymerization is preferably performed within the following range.
- the polyester film of the present invention contains 1 ppm to 30 ppm of titanium.
- the amount of the Ti-based compound is 1 ppm or more, the polymerization rate is increased and preferable IV is obtained.
- the amount of the Ti compound is 30 ppm or less, COOH can be adjusted to satisfy the above range, and a good color tone can be obtained.
- the methods described in Japanese Patent No. 340616, Japanese Patent Application Laid-Open No. 2005-239940, Japanese Patent Application Laid-Open No. 2004-319444, Japanese Patent Application Laid-Open No. 2007-204538, Japanese Patent No. 3436268, Japanese Patent No. 3780137, and the like can be applied.
- the polyester forming the polyester film (first resin layer and second resin layer) of the present invention is (A) malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, Aliphatic dicarboxylic acids such as eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, etc., adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, terephthalic acid Acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic
- the dicarboxylic acid component contains an aromatic dicarboxylic acid as a main component.
- the “main component” means that the proportion of aromatic dicarboxylic acid in the dicarboxylic acid component is 80% by mass or more.
- a dicarboxylic acid component other than the aromatic dicarboxylic acid may be included. Examples of such a dicarboxylic acid component include ester derivatives such as aromatic dicarboxylic acids.
- at least one aliphatic diol is used as the diol component.
- the aliphatic diol can contain ethylene glycol, and preferably contains ethylene glycol as a main component.
- the main component means that the proportion of ethylene glycol in the diol component is 80% by mass or more.
- polyesters are polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN), and still more preferable is PET.
- PET is preferably a PET polymerized using one or more selected from a germanium (Ge) compound, an antimony (Sb) compound, an aluminum (Al) compound, and a titanium (Ti) compound, More preferably, a Ti compound is used.
- the Ti compound has high reaction activity and can lower the polymerization temperature. Therefore, in particular, it is possible to suppress the thermal decomposition of PET during the polymerization reaction and the generation of COOH, which is suitable for adjusting the COOH amount within a predetermined range in the polyester film of the present invention.
- Ti compound examples include oxides, hydroxides, alkoxides, carboxylates, carbonates, oxalates, organic chelate titanium complexes, and halides.
- the Ti-based catalyst may be used in combination of two or more titanium compounds as long as the effects of the present invention are not impaired.
- Ti-based catalysts include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, tetraphenyl Titanium alkoxide such as titanate and tetrabenzyl titanate, titanium oxide obtained by hydrolysis of titanium alkoxide, titanium-silicon or zirconium composite oxide obtained by hydrolysis of a mixture of titanium alkoxide and silicon alkoxide or zirconium alkoxide, titanium acetate , Titanium oxalate, potassium potassium oxalate, sodium oxalate, potassium titanate, sodium titanate, titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride-aluminum chloride Miniumu mixture, titanium acetylacetonate, an organic
- At least one organic chelate titanium complex having an organic acid as a ligand can be suitably used.
- the organic acid include citric acid, lactic acid, trimellitic acid, malic acid and the like.
- an organic chelate complex having citric acid or citrate as a ligand is preferable.
- At least one of the polyester raw resin A and the recycled material B is preferably a polyester resin synthesized using a titanium citrate complex as a polymerization catalyst.
- the titanium catalyst also has a catalytic effect of the esterification reaction. By adding it at the esterification stage, the oligomer acid value at the end of the esterification reaction is lowered, and the subsequent polycondensation reaction is performed more efficiently.
- complexes with citric acid as a ligand are more resistant to hydrolysis than titanium alkoxides, etc., and do not hydrolyze in the esterification reaction process, while maintaining the original activity and catalyzing the esterification and polycondensation reactions It is estimated to function effectively as In general, it is known that as the amount of carboxyl group is increased, the hydrolysis resistance is deteriorated. By the addition method of the present invention, the amount of carboxyl group is decreased, and thus the hydrolysis resistance is expected to be improved.
- Examples of the citrate chelate titanium complex are readily available as commercial products such as VERTEC AC-420 manufactured by Johnson Matthey.
- the aromatic dicarboxylic acid and the aliphatic diol can be introduced by preparing a slurry containing them and continuously supplying it to the esterification reaction step.
- an aromatic dicarboxylic acid and an aliphatic diol are polymerized in the presence of a catalyst containing a titanium compound, and at least one of the titanium compounds is an organic chelate titanium complex having an organic acid as a ligand.
- An esterification reaction step including at least a step of adding an organic chelate titanium complex, a magnesium compound, and a pentavalent phosphate ester having no aromatic ring as a substituent in this order, and an ester formed in the esterification reaction step
- a polycondensation step in which a polycondensation product is produced by a polycondensation reaction of the polymerization reaction product, and is preferably produced by a method for producing a polyester resin.
- pentavalent phosphorus compound As the pentavalent phosphorus compound, at least one pentavalent phosphate having no aromatic ring as a substituent can be used.
- pentavalent phosphate ester in the present invention include trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, tris phosphate (triethylene glycol), methyl acid phosphate, and phosphoric acid. Examples include ethyl acid, isopropyl acid phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, and triethylene glycol acid phosphate.
- the pentavalent phosphate ester when a chelate titanium complex coordinated with citric acid or a salt thereof is used as the catalyst as the titanium compound, the pentavalent phosphate ester has better polymerization activity and color tone than the trivalent phosphate ester. Furthermore, in the case of adding a pentavalent phosphate having 2 or less carbon atoms, the balance of polymerization activity, color tone, and heat resistance can be particularly improved.
- the amount of phosphorus compound added is preferably such that the P element conversion value is in the range of 50 ppm to 90 ppm.
- the amount of the phosphorus compound is more preferably 60 ppm to 80 ppm, and still more preferably 65 ppm to 75 ppm.
- Magneium compound Inclusion of the magnesium compound improves electrostatic applicability. In this case, although it is easy to color, in this invention, coloring is suppressed and the outstanding color tone and heat resistance are obtained.
- magnesium compound examples include magnesium salts such as magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate.
- magnesium acetate is most preferable from the viewpoint of solubility in ethylene glycol.
- the Mg element conversion value is preferably 50 ppm or more, and more preferably 50 ppm or more and 100 ppm or less.
- the addition amount of the magnesium compound is preferably an amount that is in the range of 60 ppm to 90 ppm, more preferably 70 ppm to 80 ppm in terms of imparting electrostatic applicability.
- the esterification reaction may be carried out using a multistage apparatus in which at least two reactors are connected in series under conditions where ethylene glycol is refluxed while removing water or alcohol produced by the reaction from the system. it can.
- the esterification reaction described above may be performed in one stage or may be performed in multiple stages.
- the esterification reaction temperature is preferably 230 to 260 ° C, more preferably 240 to 250 ° C.
- the temperature of the esterification reaction in the first reaction tank is preferably 230 to 260 ° C, more preferably 240 to 250 ° C, and the pressure is 1.0 to 5.0 kg / cm 2 is preferable, and 2.0 to 3.0 kg / cm 2 is more preferable.
- the temperature of the esterification reaction in the second reaction tank is preferably 230 to 260 ° C., more preferably 245 to 255 ° C., and the pressure is 0.5 to 5.0 kg / cm 2 , more preferably 1.0 to 3. 0 kg / cm 2 . Furthermore, when carrying out by dividing into three or more stages, it is preferable to set the conditions for the esterification reaction in the intermediate stage to the conditions between the first reaction tank and the final reaction tank.
- a polycondensation product is produced by subjecting an esterification reaction product produced by the esterification reaction to a polycondensation reaction.
- the polycondensation reaction may be performed in one stage or may be performed in multiple stages.
- the esterification reaction product such as an oligomer generated by the esterification reaction is subsequently subjected to a polycondensation reaction.
- This polycondensation reaction can be suitably performed by supplying it to a multistage polycondensation reaction tank.
- the polycondensation reaction conditions in a three-stage reaction tank are as follows: the first reaction tank has a reaction temperature of 255 to 280 ° C., more preferably 265 to 275 ° C., and a pressure of 100 to 10 torr (13.3). ⁇ 10 ⁇ 3 to 1.3 ⁇ 10 ⁇ 3 MPa), more preferably 50 to 20 torr (6.67 ⁇ 10 ⁇ 3 to 2.67 ⁇ 10 ⁇ 3 MPa). The temperature is 265 to 285 ° C., more preferably 270 to 280 ° C., and the pressure is 20 to 1 torr (2.67 ⁇ 10 ⁇ 3 to 1.33 ⁇ 10 ⁇ 4 MPa), more preferably 10 to 3 torr (1.
- the third reaction vessel in the final reaction vessel has a reaction temperature of 270 to 290 ° C., more preferably 275 to 285 ° C., and a pressure of 10-0.1tor (1.33 ⁇ 10 -3 ⁇ 1.33 ⁇ 10 -5 MPa), aspect is preferably more preferably 5 ⁇ 0.5torr (6.67 ⁇ 10 -4 ⁇ 6.67 ⁇ 10 -5 MPa) .
- polyesters are polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN), and even more preferred is PET.
- PET polyethylene terephthalate
- PEN polyethylene-2,6-naphthalate
- a component having a total of 3 or more carboxylic acid groups and hydroxyl groups hereinafter sometimes referred to as “ ⁇ trifunctional component”
- ⁇ trifunctional component an isocyanate compound
- carbodiimide compound a carbodiimide compound
- epoxy an epoxy
- terminal blocking agent may be used alone or in combination.
- the laminated polyester film of the present invention preferably contains “ ⁇ 3 functional component”, that is, a component having a total (a + b) of carboxylic acid group (a) and hydroxyl group (b) of 3 or more.
- ⁇ 3 functional component that is, a component having a total (a + b) of carboxylic acid group (a) and hydroxyl group (b) of 3 or more.
- the component ( ⁇ trifunctional component: p) in which the sum (a + b) of the carboxylic acid group (a) and the hydroxyl group (b) is 3 or more means that the number of carboxylic acid groups (a) is 3 or more.
- carboxylic acid component as a trifunctional aromatic carboxylic acid component, trimesic acid, trimellitic acid, naphthalenetricarboxylic acid, anthracentricarboxylic acid, etc., as a trifunctional aliphatic carboxylic acid component, methanetricarboxylic acid, Ethanetricarboxylic acid, propanetricarboxylic acid, butanetricarboxylic acid, etc.
- tetrafunctional aromatic carboxylic acid constituents such as benzenetetracarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, naphthalenetetracarboxylic acid, anthracenetetracarboxylic acid, berylene Tetracarboxylic acid is a tetrafunctional aliphatic carboxylic acid component, Acid, ethylenetetracarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, adamantanetetracarboxylic acid, etc.
- benzenepentacarboxylic acid such as benzenepentacarboxylic acid, benzenehexacarboxylic acid.
- carboxylic acid constituents ethanepentacarboxylic acid, ethanehexacarboxylic acid, butanepentacarboxylic acid, butaneheptacarboxylic acid, cyclopentanepentacarboxylic acid, cyclohexane San penta carboxylic acid, cyclohexanehexacarboxylic acid, adamantane penta carboxylic acid, and adamantane hexacarboxylic acid., As well as such as the ester derivatives thereof and acid anhydrides thereof as examples without limitation.
- oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid and the like, or a combination of a plurality of such oxyacids to the carboxy terminal of the carboxylic acid component. Used. Moreover, these may be used independently or may be used in multiple types as needed.
- Examples of the component (p) having 3 or more hydroxyl groups (b) include trifunctional benzene, trihydroxybenzene, trihydroxynaphthalene, trihydroxyanthracene, trihydroxychalcone, and trihydroxyflavone. , Trihydroxycoumarin, trifunctional aliphatic alcohol component (p) as glycerin, trimethylolpropane, propanetriol, tetrafunctional aliphatic alcohol component as a compound such as pentaerythritol, and hydroxyl group of the above compound
- the component (p) in which a diol is added to the terminal is also preferably used. Moreover, these may be used independently or may be used in multiple types as needed.
- oxyacids having both a hydroxyl group and a carboxylic acid group in one molecule such as hydroxyisophthalic acid, hydroxyterephthalic acid, dihydroxyterephthalic acid, and dihydroxyterephthalic acid, and the number of carboxylic acid groups ( The total (a + b) of a) and the number of hydroxyl groups (b) is 3 or more.
- oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of such oxyacids added to the carboxy terminus of the above-described constituents are also preferably used. . Moreover, these may be used independently or may be used in multiple types as needed.
- the content of the constituent component is preferably 0.005 mol% or more and 2.5 mol% with respect to all the constituent components in the laminated polyester film. . More preferably, it is 0.020 mol% or more and 1 mol% or less, More preferably, it is 0.025 mol% or more and 1 mol% or less, More preferably, it is 0.035 mol% or more and 0.5 mol% or less, More preferably, it is 0.05.
- the mol% is 0.5 mol% or less, particularly preferably 0.1 mol% or more and 0.25 mol% or less.
- the functional group that has not been used for polycondensation can be further improved in adhesion by hydrogen bonding and covalent bonding with the component in the coating layer.
- Such a synergistic effect can be obtained by using the ⁇ 3 functional component in combination with the polyester film substrate having the crystallinity distribution of the present invention. That is, the material of the coating layer that penetrates into a place having a low degree of crystallinity forms a bond with the functional group and improves the adhesion. At this time, by penetrating, the number of reaction with the functional group is further increased compared to the reaction only on the surface, and the adhesion is easily increased.
- the amount of the ⁇ 3 functional component (p) is 0.005 mol% or more, the adhesion is further improved.
- the amount of the ⁇ 3 functional component (p) is 2.5 mol% or less, crystals are formed in the polyester, the strength is hardly lowered, and as a result, the cohesive failure is hardly exhibited and the adhesion is improved. Can do.
- the polyester in the present invention can further contain additives such as a terminal blocking agent, a light stabilizer, and an antioxidant.
- a terminal blocking agent is added to at least one of the polyester resins A1, A2, and B in the present invention.
- a terminal blocking agent By containing a terminal blocking agent, the amount of carboxyl groups can be reduced, and the hydrolysis resistance can be improved.
- the terminal blocker preferably contains at least one terminal blocker of an isocyanate compound, a carbodiimide compound, or an epoxy compound. Particularly preferred are epoxy compounds and carbodiimide compounds.
- the end-capping agent is generally a bifunctional or higher functional compound.
- the compounding amount increases, the molecular chains of the polyester are cross-linked, gelled, and become unmelted when melt-extruded. Adversely affects film quality. Therefore, it is particularly preferable to use a monofunctional end capping agent, and a monofunctional epoxy compound is particularly preferable.
- the content of the end-capping agent in the polyester film is preferably 0.1% by mass or more and 7% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less with respect to the total mass of the polyester film. More preferably, it is 0.7 mass% or more and 3 mass% or less.
- the polyester resin A of the present invention preferably has a light stabilizer added thereto.
- a light stabilizer By containing the light stabilizer, it is possible to prevent ultraviolet degradation.
- the light stabilizer include a compound that absorbs light such as ultraviolet rays and converts it into thermal energy, a material that absorbs light and decomposes when the film or the like absorbs light, and a material that suppresses the decomposition chain reaction. .
- the light stabilizer is preferably a compound that absorbs light such as ultraviolet rays and converts it into heat energy.
- a light stabilizer in the film, it becomes possible to keep the effect of improving the partial discharge voltage by the film high for a long time even if the film is irradiated with ultraviolet rays continuously for a long time. Changes in color tone, strength deterioration, and the like due to UV rays.
- an ultraviolet absorber is a range in which other properties of the polyester are not impaired, any of organic ultraviolet absorbers, inorganic ultraviolet absorbers, and combinations thereof are preferably used without particular limitation. Can do. On the other hand, it is desired that the ultraviolet absorber is excellent in moisture and heat resistance and can be uniformly dispersed in the film.
- ultraviolet absorbers include, for example, salicylic acid-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based ultraviolet absorbers, hindered amine-based ultraviolet stabilizers, and the like as organic ultraviolet absorbers.
- salicylic acid-based pt-butylphenyl salicylate p-octylphenyl salicylate
- benzophenone-based 2,4-dihydroxybenzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy -5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane
- benzotriazole 2- (2'-hydroxy-5) '-Methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H benzotriazol-2-yl) phenol], a cyanoacrylate Ethyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate), 2- (4,6
- triazine-based ultraviolet absorbers are more preferable in that they have high resistance to repeated ultraviolet absorption.
- these ultraviolet absorbers may be added to the above-mentioned ultraviolet absorber alone, or a form in which an organic conductive material or a water-insoluble resin is copolymerized with a monomer having an ultraviolet absorber ability. May be introduced.
- the content of the light stabilizer in the polyester film is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 7% by mass or less with respect to the total mass of the polyester film. More preferably, it is 0.7 mass% or more and 4 mass% or less.
- the polyester film of the present invention includes, for example, a lubricant (fine particles), an ultraviolet absorber, a colorant, a heat stabilizer, a nucleating agent (crystallization agent), and a flame retardant. Etc. can be contained as additives.
- the recycled material B examples include a pulverized polyester and a recycled material obtained by remelting the recovered polyester.
- a raw material resin for forming the core layer in addition to polyester A2, recycled material B having an intrinsic viscosity (IV) of 0.55 to 0.80 and a carboxyl group content (AV) of 35 equivalents / ton or less is 10 to
- the content of the recycled material B with respect to the total amount of the mixed raw material resin is preferably 15 to 40% by mass, more preferably 20 to 40% by mass, from the viewpoint of hydrolysis resistance of the entire laminated film.
- -IV- Recycled material B used for forming the core layer is blended when IV is less than 0.55 and decreases the mechanical properties of the laminated film, and when it exceeds 0.80, the effect of decreasing the melt viscosity during melt extrusion is reduced.
- the shear heating value increases, the thermal decomposition proceeds to increase the AV value, and the hydrolysis resistance of the laminated film decreases.
- the IV of the recycled material is preferably 0.60 to 0.80, and more preferably 0.60 to 0.75.
- the difference ⁇ IV between the intrinsic viscosity of the recycled material B and the intrinsic viscosity of the polyester resin A (A2) (IV of the polyester resin A2 ⁇ IV of the recycled material B) is 0. It is preferably from 05 to 0.3. By setting it within the range of this difference, an increase in the amount of carboxyl groups can be further suppressed by suppressing heat generation during extrusion, and the mechanical properties of the obtained laminated polyester film can be maintained.
- ⁇ IV is more preferably 0.05 to 0.2, and further preferably 0.05 to 0.18.
- the recycled material B used for forming the core layer has an excessively high AV value for the blended film, resulting in poor hydrolysis resistance.
- the AV of the recycled material B is preferably 30 equivalents / ton or less.
- the melting point Tm of the recycled material B is preferably in the range of 255 ° C. to 260 ° C.
- the recycled material B is contained in the range of 10 to 40% by mass with respect to the total mass of the mixed raw material resin, and the difference in intrinsic viscosity ⁇ IV between the recycled material B and the polyester resin A2 is 0.05 to More preferably, it is 0.2, and more preferably, the recycled material B is contained in the range of 15 to 35% by mass with respect to the total mass of the mixed raw material resin, and between the recycled material B and the polyester resin A2.
- the intrinsic viscosity difference ⁇ IV is set to 0.05 to 0.18.
- the polyester raw resin A1 is dried to a water content of 100 ppm or less.
- the polyester raw material resin A1 after the solid phase polymerization step is dried at 140 to 170 ° C. for 2 to 8 hours using, for example, heated nitrogen having a dew point temperature of ⁇ 30 ° C.
- the water content of the raw material resin can be measured by a Karl Fischer moisture meter (MKC-520, manufactured by Kyoto Electronics Industry Co., Ltd.).
- the mixed raw material resin containing the polyester raw material resin A2 and the recycled material B and having a ratio of the recycled material B to the total weight of the polyester resin of 15 to 40% by mass is dried to a water content of 100 ppm or less. For example, it is dried at 140 to 170 ° C. for 2 to 8 hours using heated nitrogen having a dew point temperature of ⁇ 30 ° C.
- the extruder used for melt extrusion of each raw material resin is not particularly limited, and a single screw extruder, a twin screw extruder, or the like can be used. In the present invention, a twin screw extruder can be preferably used. .
- FIG. 1 schematically shows an example of the configuration of a twin-screw extruder used in carrying out the method for producing a polyester film according to the present invention.
- FIG. 2 shows an example of a flow for carrying out the method for producing a polyester film according to the present invention.
- the twin-screw extruder shown in FIG. 1 is disposed around a cylinder 10 (barrel) having a supply port 12 and an extruder outlet 14, two screws 20A and 20B rotating in the cylinder 10, and the cylinder 10 Temperature control means 30 for controlling the temperature in the cylinder 10.
- a raw material supply device 46 is provided in front of the supply port 12. Further, a gear pump 44, a filter 42, and a die 40 are provided at the tip of the extruder outlet 14 as shown in FIG.
- the cylinder 10 has a supply port 12 for supplying the raw material resin and an extruder outlet 14 through which the heat-melted resin is extruded.
- a material that is excellent in heat resistance, wear resistance, and corrosion resistance and that can ensure friction with the resin.
- nitrided steel whose inner surface is nitrided is used, but chromium molybdenum steel, nickel chromium molybdenum steel, and stainless steel can also be nitrided and used.
- a bimetallic cylinder in which a corrosion-resistant and wear-resistant material alloy such as nickel, cobalt, chromium or tungsten is lined on the inner wall surface of the cylinder 10 by centrifugal casting. It is effective to use or form a ceramic sprayed coating.
- a corrosion-resistant and wear-resistant material alloy such as nickel, cobalt, chromium or tungsten
- the cylinder 10 is provided with vents 16A and 16B for drawing a vacuum. By evacuating through the vents 16A and 16B, volatile components such as moisture in the resin in the cylinder 10 can be efficiently removed.
- volatile components such as moisture in the resin in the cylinder 10
- the vents 16A and 16B are required to have an appropriate opening area and number of vents in relation to the deaeration efficiency.
- the twin-screw extruder 100 used in the present invention desirably has one or more vents 16A and 16B.
- vents 16A and 16B are too large, there is a concern that the molten resin may overflow from the vent and there is a concern that the staying deterioration foreign matter may increase. Therefore, it is preferable to provide one or two vents.
- the resin staying on the wall surface near the vent or the deposited volatile component falls into the extruder 100 (cylinder 10), it may be manifested as a foreign substance in the product, so care must be taken.
- optimization of the shape of the vent lid and appropriate selection of the upper vent and the side vent are effective, and precipitation of volatile components is generally performed by a method of preventing precipitation by heating the piping or the like.
- oxidative decomposition can be suppressed by evacuating the resin supply port 12 or performing a nitrogen purge. Further, by providing the vents 16A and 16B at a plurality of locations, even when the raw material moisture content is about 2000 ppm, the same extrusion as when the resin dried to 50 ppm or less is extruded on a single axis is possible.
- the vent pressure is preferably 0.01 Torr to 5 Torr (1.333 Pa to 666.5 Pa). More preferably, the pressure is set at 01 Torr to 4 Torr (1.333 Pa to 533.2 Pa).
- two screws 20 ⁇ / b> A and 20 ⁇ / b> B that are rotated by a driving unit 21 including a motor and a gear are provided.
- the screw diameter D is preferably 30 to 250 mm or less, and more preferably 50 to 200 mm or less.
- the twin screw extruder is roughly divided into a meshing type and a non-meshing type of the two screws 20A and 20B, and the meshing type has a larger kneading effect than the non-meshing type.
- any of a meshing type and a non-meshing type may be used, but it is preferable to use a meshing type from the viewpoint of sufficiently kneading the raw material resin and suppressing melting unevenness.
- the rotation directions of the two screws 20A and 20B are also divided into the same direction and different directions, respectively.
- the different-direction rotating screws 20A and 20B have a higher kneading effect than the same-direction rotating type, and the same-direction rotating type has a self-cleaning effect, which is effective for preventing retention in the extruder. Furthermore, the axial direction is also parallel and oblique, and there is also a conical type shape used when applying strong shear.
- screw segments having various shapes can be used.
- As the shape of the screws 20 ⁇ / b> A and 20 ⁇ / b> B for example, a full flight screw provided with a single spiral flight 22 having an equal pitch is used.
- a segment that imparts shear such as a kneading disk or a rotor, in the heating and melting part, the raw material resin can be more reliably melted.
- a reverse screw or a seal ring it is possible to dam the resin and form a melt seal when pulling the vents 16A and 16B.
- kneading parts 24A and 24B that promote melting of the raw material resin as described above can be provided in the vicinity of the vents 16A and 16B.
- a temperature control zone for cooling the molten resin is effective.
- the heat transfer efficiency of the cylinder 10 is higher than the shear heat generation, for example, by providing a screw 28 with a short pitch in the temperature control zone (cooling section), the resin moving speed of the wall surface of the cylinder 10 is increased and the temperature control efficiency is increased. Can do.
- a temperature control means 30 is provided around the cylinder 10.
- heating / cooling devices C1 to C9 divided into nine in the longitudinal direction from the raw material supply port 12 to the extruder outlet 14 constitute the temperature control means 30.
- the heating / cooling devices C1 to C9 arranged separately around the cylinder 10 are divided into, for example, heating / melting parts C1 to C7 and cooling parts C8 and C9, and the inside of the cylinder 10 is divided. Each region can be controlled to a desired temperature.
- the heating is usually performed using a band heater or a sheathed wire aluminum cast heater, but is not limited thereto, and for example, a heating medium circulating heating method can also be used.
- air cooling by a blower is generally used for cooling, but there is also a method of flowing water or oil through a pipe (water passage) wound around the cylinder 10.
- a die 40 is provided at the extruder outlet 14 of the cylinder 10 for discharging the molten resin extruded from the extruder outlet 14 into a film (strip shape). Further, a filter 42 is provided between the extruder outlet 14 of the cylinder 10 and the die 40 to prevent unmelted resin and foreign matter from entering the film.
- a gear pump 44 may be provided between the extruder 100 and the die 40 in order to reduce the variation in the extrusion amount as much as possible. By supplying a certain amount of resin from the gear pump 44, the thickness accuracy can be improved. In particular, when using a twin screw extruder, it is preferable to stabilize the extrusion by the gear pump 44 because the pressurization capacity of the extruder itself is low.
- the pressure fluctuation on the secondary side of the gear pump 44 can be reduced to 1/5 or less on the primary side, and the resin pressure fluctuation range can be within ⁇ 1%.
- the gear pump 44 is installed, the length of the equipment becomes long depending on the equipment selection method, and the residence time of the resin becomes long, and the shearing stress of the gear pump section may cause the molecular chain to be broken. It is.
- the differential pressure during operation is set to 20 MPa or less, preferably 15 MPa, and more preferably 10 MPa or less. In order to make the film thickness uniform, it is also effective to control the screw rotation of the extruder or to use a pressure control valve in order to keep the primary pressure of the gear pump 44 constant.
- the cylinder 10 is heated by the temperature control means 30 and the screw is rotated, and the polyester resin raw material (raw material resin) is supplied from the supply port 12.
- the supply port 12 is preferably cooled to prevent heat transfer of the raw material resin pellets and the like, and to protect the screw drive equipment such as the motor.
- the raw material resin supplied into the cylinder is melted not only by heating by the temperature control means 30, but also by heat generated by friction between the resins accompanying rotation of the screws 20A and 20B, friction between the resin and the screws 20A and 20B and the cylinder 10, and the like. And gradually moves toward the extruder outlet 14 as the screw rotates.
- the raw material resin supplied into the cylinder is heated to a temperature equal to or higher than the melting point Tm (° C.).
- Tm melting point
- COOH may increase remarkably due to thermal decomposition, leading to a decrease in hydrolysis resistance.
- the resin and the resin are coextruded, they are coextruded so that the temperature of the molten resin extruded from the T die is 280 to 300 ° C.
- the molten resin temperature means a temperature at which the molten resin extruded from the T die is measured by a contact thermometer.
- the melt extrusion is performed by adjusting the heating temperature by the temperature control means 30 and the rotation speed of the screws 20A and 20B to control the molten resin temperature in the range of 280 to 300 ° C.
- the molten resin temperature is less than 280 ° C.
- a part of the molten resin is solidified to generate an unmelted resin.
- the molten resin temperature exceeds 300 ° C.
- COOH increases due to thermal decomposition, and hydrolysis resistance tends to decrease.
- the inside of the extruder is replaced with nitrogen from the viewpoint that generation of COOH due to thermal decomposition can be further suppressed.
- the molten resin temperature of the first molten resin obtained by melting the polyester raw resin A1 for forming the skin layer is preferably 285 to 300 ° C, and more preferably 285 to 295 ° C.
- the molten resin temperature of the second molten resin obtained by melting the mixed raw material resin of the recycled material B and the polyester raw material resin A2 for forming the core layer is preferably 280 to 300 ° C, and preferably 280 to 290 ° C. It is more preferable.
- the molten resin temperature of the hanging curtain when the skin layer and the core layer are merged and extruded from the T die is preferably 280 to 300 ° C., more preferably 280 to 295 ° C.
- the thickness of the film of the second molten resin is greater than the thickness of the film of the first molten resin, and the first molten resin and the second molten resin that are melt-extruded In a state where the molten resin film is laminated on at least one surface of the second molten resin film, the molten resin film is cooled and solidified on a cast roll to form a laminate composed of at least two layers.
- Resin (first molten resin and second molten resin) extruded from the extruder outlet 14 of the cylinder 10 is passed through a gear pump 44 and a filter 42 and extruded from a die 40 onto a cast roll (cooling roll) to form a film. Mold.
- the thickness of the second molten resin film is larger than the thickness of the first molten resin film, and the first molten resin film is laminated on at least one surface of the second molten resin film.
- the first molten resin film may be laminated on one side of the second molten resin film to have a two-layer structure, or may be laminated on both sides to have a three-layer structure.
- the humidity it is preferable to adjust the humidity to 5% RH to 60% RH (Relative Humidity) between extrusion of each melt (molten resin) from the die 40 and contact with the cast roll (air gap). More preferably, it is adjusted to 15% RH to 50% RH.
- RH relative Humidity
- Each melt coextruded from the extrusion die is cooled and solidified using a cast roll (cooling roll).
- the temperature of the cast roll is preferably 10 ° C or higher and 80 ° C or lower, more preferably 15 ° C or higher and 70 ° C or lower, and further preferably 20 ° C or higher and 60 ° C or lower.
- the first molten resin film serving as the skin layer is formed to be thinner than the second molten resin film serving as the core layer.
- the thickness ratio of the first molten resin film to the second molten resin film is preferably 1/150 to 1/4, and more preferably 1/100 to 1/8.
- the polyester resin A is used, and the time required for the extruded melt to cool below the glass transition temperature (Tg) is reduced by reducing the thickness of the first molten resin film that has a small AV value and is easily crystallized. Can be shortened. As a result, crystallization of the skin layer is suppressed and the transparency of the laminated film is improved.
- Tg represents a glass transition temperature and can be measured based on JIS K7121 or ASTM D3418-82.
- the overall thickness of the unstretched laminate is preferably 500 to 4000 ⁇ m. If the thickness of the entire laminate is less than 500 ⁇ m, the thickness of the skin layer becomes too thin, and the skin layer cannot be laminated on the core layer uniformly in the width direction. On the other hand, when the thickness of the entire laminate exceeds 4000 ⁇ m, the thickness unevenness becomes large, crystallization progresses, and stretching becomes difficult, and even if stretched, the accuracy of thickness unevenness may be reduced.
- the laminate (unstretched laminated polyester film) produced by the molding step is stretched in the longitudinal direction (MD) and the width direction (TD) to perform biaxial stretching (longitudinal stretching and lateral stretching).
- the laminate is led to a group of rolls heated to a temperature of 70 ° C. or more and 140 ° C. or less, and stretched in a longitudinal direction (longitudinal direction, that is, a traveling direction of the film) at a stretch ratio of 3 to 5 times, It cools with the roll group of the temperature below 50 degreeC. Subsequently, the film is guided to a tenter while gripping both ends of the film with a clip, and in an atmosphere heated to a temperature of 80 ° C. or higher and 150 ° C. or lower, the direction perpendicular to the longitudinal direction (width direction) is 3 to 5 times. Stretch at a stretch ratio.
- the stretching rate is preferably 3 to 5 times in each of the longitudinal direction and the width direction.
- the area magnification (longitudinal stretch magnification x lateral stretch magnification) is 9 times or more and 15 times or less.
- the area magnification is 9 times or more, the reflectance, concealability and film strength of the obtained biaxially stretched laminated polyester film are good, and when the area magnification is 15 times or less, tearing during stretching is avoided. be able to.
- the simultaneous biaxial stretching method in addition to the sequential biaxial stretching method in which the longitudinal direction and the width direction are separated separately, the simultaneous biaxial stretching method in which the longitudinal direction and the width direction are simultaneously stretched. Either may be sufficient.
- stretching used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal and transverse stretching, and transverse / longitudinal stretching may be performed. The order of longitudinal stretching and lateral stretching may be reversed.
- the biaxially stretched film was heat-set in the tenter, and after uniform cooling, Cool to room temperature.
- Ts heat setting treatment temperature
- the heat treatment temperature is preferably high.
- the heat treatment temperature is preferably 150 to 250 ° C., more preferably 180 to 230 ° C.
- a relaxation (relaxation) treatment of 1 to 12% may be performed in the width direction or the longitudinal direction.
- the heat-set polyester film is usually cooled to Tg or less, and the clip gripping portions at both ends of the polyester film are cut and wound into a roll.
- the cooling is preferably performed by gradually cooling from the final heat setting temperature to room temperature at a cooling rate of 1 ° C. to 100 ° C. per second.
- Tg at a cooling rate of 1 ° C. or more and 100 ° C. or less per second.
- means for cooling and relaxation treatment it is preferable to perform these treatments while sequentially cooling in a plurality of temperature regions, particularly in terms of improving the dimensional stability of the polyester film.
- the first polyester layer (skin layer) having an intrinsic viscosity of 0.55 to 0.80 and a carboxyl group amount of 7 to 25 equivalents / ton, and the total mass 10 to 40% by mass of a polyester resin recycled material, an intrinsic viscosity of 0.55 to 0.76, an amount of carboxyl groups of 8 to 30 equivalents / ton, and the first Biaxially made of polyester having a laminated structure including a second polyester layer (core layer) thicker than the polyester layer, having an intrinsic viscosity of 0.55 or more and a carboxyl group content of 30 equivalents / ton or less
- An oriented laminated polyester film can be produced.
- a three-layer structure including a second polyester layer and two first polyester layers sandwiching the second polyester layer that is, a laminated polyester in which skin layers are laminated on both sides of the core layer, respectively. It can also be a film.
- the laminated polyester film produced according to the present invention is excellent in electrical insulation, small in thickness unevenness, and excellent in hydrolysis resistance under high temperature and high humidity.
- Polyester film for battery members specifically, for use as a back protective sheet (so-called solar battery back sheet) disposed on the back surface opposite to the solar light incident side of a solar cell power generation module, a barrier film substrate, etc. Is preferred.
- the power generation element (solar cell element) connected by the lead wiring for taking out electricity is sealed with a sealing agent such as ethylene / vinyl acetate copolymer system (EVA system) resin,
- EVA system ethylene / vinyl acetate copolymer system
- solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and group III-V such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- group III-V such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenic.
- Various known solar cell elements such as II-VI group compound semiconductor systems can be applied.
- Example 1 -Twin screw extruder- As shown in FIG. 1, the extruder is provided with a screw having the following configuration in a cylinder provided with vents at two locations as shown in FIG. 1, and the temperature can be controlled by dividing the cylinder into nine zones in the longitudinal direction.
- a double vent type co-rotating mesh type twin screw extruder equipped with a heater (temperature control means) was prepared.
- Screw shape plasticization kneading section just before the first vent, degassing promotion kneading section just before the second vent
- gear pump 2-gear type Filter: Sintered metal fiber filter (pore diameter 20 ⁇ m) Die: Lip spacing 4mm
- polyester resin A pellets of polyethylene terephthalate (intrinsic viscosity IV: 0.8 dl / g, COOH amount AV: 13 eq / t, water content after drying: 45 ppm) produced using a Ti-citric acid complex as a catalyst ( PET1) was prepared.
- a recycled chip 1 made of polyethylene terephthalate (ultimate viscosity IV: 0.76 dl / g, COOH amount AV: 15 eq / t, moisture content after drying: 48 ppm) was prepared.
- a body unstretched film
- the barrel set temperature of each extruder was set to 280 ° C., and the screw rotation speed was set to 80 rpm.
- Each raw material was supplied from the supply port, heated and melted, and melt extrusion was performed.
- the temperature of the molten resin extruded from the T die was 291 ° C.
- the melt (melt) extruded from the extruder outlet was passed through a gear pump and a metal fiber filter (pore diameter 20 ⁇ m), and then extruded from a die to a cooling (chill) roll.
- the extruded melt was brought into close contact with the cooling roll using an electrostatic application method.
- As the cooling roll a hollow cast roll is used, and the temperature can be adjusted by passing water as a heating medium.
- the conveyance area (air gap) from the die exit to the cooling roll surrounds this conveyance area, and humidity is adjusted to 30% RH by introducing humidity-conditioned air therein.
- the melt thickness was about 3300 ⁇ m on average.
- Example 2 A polyester film was produced and evaluated in the same manner as in Example 1 except that the raw materials and extrusion conditions were changed as shown in Table 1.
- Catalyst 1 is a Ti-citric acid complex (manufactured by Johnson Matthey, VERTEC AC-420), and “Catalyst 2” is TiO 2 (manufactured by Sumitomo Metal Industries).
- a carbodiimide compound “Tabakuzol P100” manufactured by Rhein Chemie
- an epoxy compound “Cardura E10P” manufactured by Hexion Specialty Chemicals were used as end-capping agents, respectively. Added to the extruder and compounded.
- Example 1 the thickness unevenness was small, and the weather resistance (hydrolysis resistance) was excellent.
- Comparative Example 1 in which the recycled chip was not used for forming the core layer, the shear heat generation in the extrusion process was large, the molten resin temperature exceeded 300 ° C., and the decrease in IV and the increase in AV were large. As a result, hydrolysis resistance decreases.
- Comparative Example 5 a material having a small intrinsic viscosity and a large amount of carboxyl groups was used as the recycled material B. As a result, the amount of carboxyl groups in the film exceeded 30 eq / ton, and the hydrolysis resistance decreased. Other non-uniform thickness and surface irregularities were also aggravated.
- Comparative Example 6 a material having a high intrinsic viscosity and a small amount of carboxyl groups was used as the recycled material B. As a result, the melt viscosity in the extruder was increased. As a result, the amount of heat generated by shearing was increased, the thermal decomposition proceeded, and the film was colored. Further, in the core portion that takes time to cool, as a result of the thermal decomposition of the raw material, the molecular mobility increased, the crystallization rate increased, and haze increased due to crystallization. In addition, the difference in melt viscosity between the skin and the core layer was large, surface unevenness was similarly generated, the amount of carboxyl groups exceeded 30 eq / ton, and the hydrolysis resistance decreased.
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Abstract
Description
また、末端封止材の配合による方法では、溶融粘度の増加は少ないもののゲル化による異物が発生し、面状を荒らす懸念がある。特に、コスト低減等を目的としてポリエステルのリサイクル原料を用いてポリエステルフィルムを製造する場合(例えば、特開平7-323511号公報参照)に上記のような懸念が顕著になる。
<1> 極限粘度が0.60~0.85であり、カルボキシル基量が5~20当量/トンであるポリエステル原料樹脂A1及びA2とからなるポリエステル原料樹脂Aと、極限粘度が0.55~0.80であり、カルボキシル基量が35当量/トン以下であるポリエステル樹脂のリサイクル材Bを準備する原料準備工程と、
前記ポリエステル原料樹脂A1を、100ppm以下の含水量に乾燥させる第1の乾燥工程と、
前記ポリエステル原料樹脂A2及び前記リサイクル材Bを含み、ポリエステル樹脂の合計質量に対する前記リサイクル材Bの割合が10~40質量%である混合原料樹脂を、100ppm以下の含水量に乾燥させる第2の乾燥工程と、
前記第1の乾燥工程で乾燥された前記ポリエステル原料樹脂A1を溶融した第1の溶融樹脂と、前記第2の乾燥工程で乾燥された前記混合原料樹脂を溶融した第2の溶融樹脂とを共押出する際、それぞれTダイから押出された溶融樹脂温度が280~300℃となる溶融押出工程と、
溶融押出された前記第1の溶融樹脂及び前記第2の溶融樹脂を、前記第2の溶融樹脂の膜の厚みが前記第1の溶融樹脂の膜よりも厚く、かつ、前記第1の溶融樹脂の膜が前記第2の溶融樹脂の膜の少なくとも一方の面に積層した状態でキャストロール上にて冷却固化し、少なくとも2層からなる積層体を成形する成形工程と、
前記積層体を長手方向及び幅方向に延伸する二軸延伸工程と、
を有する積層ポリエステルフィルムの製造方法。
<2> 前記ポリエステル原料樹脂A及び前記リサイクル材Bの少なくとも一方は、チタン化合物を重合触媒として合成されたポリエステル樹脂である<1>に記載の積層ポリエステルフィルムの製造方法。
<3> 前記チタン化合物が少なくとも一種の有機酸を配位子とする有機キレートチタン錯体を含む<2>に記載の積層ポリエステルフィルムの製造方法。
<4> 前記溶融押出工程において、前記第1溶融樹脂及び前記第2溶融樹脂の少なくとも一方に、エポキシ化合物又はカルボジイミド化合物から選ばれる少なくとも1種の末端封止剤を積層ポリエステルフィルム全質量に対して0.1質量%以上5質量%以下配合する<1>~<3>に記載の積層ポリエステルフィルムの製造方法。
<5> 前記成形工程は、溶融押出された前記第2の溶融樹脂の膜を、溶融押出された前記第1の溶融樹脂の膜で挟んだ積層状態でキャストロール上で冷却固化し、3層からなる積層構造の積層体を成形する<1>~<4>に記載の積層ポリエステルフィルムの製造方法。
<6> 5~20℃/minの昇温速度での示差走査熱量測定による前記ポリエステル原料樹脂Aの融点Tmが、250℃~265℃の範囲である<1>~<5>のいずれか一に記載の積層ポリエステルフィルムの製造方法。
<7> 極限粘度が0.55~0.80であり、カルボキシル基量が7~25当量/トンである第1のポリエステル層、及び全質量に対して10~40質量%のポリエステル樹脂のリサイクル材を含んで形成され、極限粘度が0.55~0.76であり、カルボキシル基量が8~30当量/トンであると共に、前記第1のポリエステル層の厚みより厚い第2のポリエステル層を含む積層構造を有し、<1>~<6>のいずれかに記載のポリエステルフィルムの製造方法により作製された、極限粘度が0.55以上であってカルボキシル基量が30当量/トン以下であるポリエステルからなる積層ポリエステルフィルム。
<8> 前記積層構造は、前記第2のポリエステル層と、前記第2のポリエステル層を挟む2層の前記第1のポリエステル層とを含む3層構造である<7>に記載の積層ポリエステルフィルム。
<9> <7>又は<8>に記載された積層ポリエステルフィルムを備えた太陽電池用バックシート。
<10> <9>に記載された太陽電池用バックシートを備えた太陽電池モジュール。
そのため、厚みが異なるポリエステル樹脂の溶融膜を共押出しによって積層フィルムを製造する場合、極限粘度が小さく、かつ、各樹脂間の極限粘度の差が小さい原料樹脂を用いて厚みの薄いフィルムを共押出して未延伸フィルムを製造することが一般的であり、極限粘度が比較的高い原料樹脂を用いて共押出しした後、二軸延伸して厚み精度が高い積層フィルムを製造することは困難であった。
また、極限粘度が高いほど、溶融押出しにおけるせん断発熱量が増加するため、溶融樹脂の温度が高くなり、熱分解を起こす。その結果、極限粘度が低下、カルボキシル基量も増加する。その結果、湿熱環境下でポリエステルフィルムを使用した際の機械強度が低下してしまい、耐加水分解性が低下してしまう。
尚、溶融粘度は、JIS K7210、或いはK7390附属書2等に基づいて測定することができる。
極限粘度が0.60~0.85であり、カルボキシル基量が5~20当量/トンであるポリエステル原料樹脂A1及びA2と、極限粘度が0.55~0.80であり、カルボキシル基量が35当量/トン以下であるポリエステル樹脂のリサイクル材Bを準備する原料準備工程と、
前記ポリエステル原料樹脂A1を、100ppm以下の含水量に乾燥させる第1の乾燥工程と、
前記ポリエステル原料樹脂A2及び前記リサイクル材Bを含み、ポリエステル樹脂の合計質量に対する前記リサイクル材Bの割合が10~40質量%である混合原料樹脂を、100ppm以下の含水量に乾燥させる第2の乾燥工程と、
前記第1の乾燥工程で乾燥された前記ポリエステル原料樹脂A1を溶融した第1の溶融樹脂と、前記第2の乾燥工程で乾燥された前記混合原料樹脂を溶融した第2の溶融樹脂とを共押出する際、それぞれTダイから押出された溶融樹脂温度が280~300℃となる溶融押出工程と、
溶融押出された前記第1の溶融樹脂及び前記第2の溶融樹脂を、前記第2の溶融樹脂の膜の厚みが前記第1の溶融樹脂の膜よりも厚く、かつ、前記第1の溶融樹脂の膜が前記第2の溶融樹脂の膜の少なくとも一方の面に積層した状態でキャストロール上で冷却固化し、少なくとも2層からなる積層体を成形する成形工程と、
前記積層体を長手方向及び幅方向に延伸する二軸延伸工程と、
を有する。
以下、各工程について説明する。
まず、極限粘度が0.60~0.85であり、カルボキシル基量が5~20当量/トンであるポリエステル原料樹脂A1及びA2と、極限粘度が0.55~0.80であり、カルボキシル基量が35当量/トン以下であるポリエステル樹脂のリサイクル材Bを準備する。
ポリエステル原料樹脂A1は、製造する積層ポリエステルフィルムの最表面層となる厚みが薄い層(「スキン層」と称する場合がある。)を形成するために使用され、ポリエステル原料樹脂A2とリサイクル材Bは、スキン層よりも厚く、積層ポリエステルフィルムの基材となる層(「コア層」と称する場合がある。)を形成するために使用される。
ポリエステル原料樹脂A1、A2として、極限粘度(IV)が0.60~0.85であり、カルボキシル基量(AV)が5~20当量/トンであるポリエステル樹脂を用意する。原料樹脂A1とA2は、極限粘度(IV)が0.60~0.85であり、カルボキシル基量(AV)が5~20当量/トンであれば、同じ材料でもよいし、異なる材料でもよい。以下、ポリエステル原料樹脂A1、A2をまとめて「ポリエステル原料樹脂A」と記す場合がある。
原料樹脂のIVは、重合方式および重合条件によって調整することができる。具体的には、液相重合の後に固相重合を行う際、処理温度、処理時間、処理雰囲気水分、酸素濃度の調節によって極限粘度IVが0.60~0.85のポリエステル樹脂を得ることができる。
ポリエステル樹脂の溶融押出工程では、せん断で発熱し易く、熱分解によりカルボキシル基量が増加し易いが、IVが0.60~0.85にあるポリエステル樹脂を用いれば、加熱溶融部において原料樹脂を十分混練して極端なせん断発熱を起こさせることなく、溶融させることができるとともに、カルボキシル基量の増加を効果的に抑制することができる。
IVが0.60未満である場合、カルボキシル基量が20当量/トン以下の原料ペレットを得ることができず、高度な耐加水分解性が得られない。一般的にポリエステルの重合反応では低温で重合した場合、カルボキシル基量を低く抑えることができることは知られている。但し、反応温度を低くした場合、重合時間が長くなり着色、生産性(コスト)が悪化するため、一定の範囲内で製造されている。0.85を超えると、溶融押出時のせん断発熱量が多くなり、溶融粘度が変動してしまうばかりでなく、熱分解によってカルボキシル基量が大きく上昇してしまう。
ポリエステル原料樹脂Aは、極限粘度(IV)が0.60~0.80であることが好ましく、0.70~0.80であることがさらに好ましい。
ポリエステル原料樹脂AのAVは、重合方式および重合条件によって調整することができる。具体的には、液相重合の後に固相重合を行う際、処理温度、処理時間、処理雰囲気水分、酸素濃度の調節によってカルボキシル基量(AV)が5~20当量/トンのポリエステル樹脂を得ることができる。
ポリエステル原料樹脂AのAVが5当量/トン未満であると、分子鎖の直線性が高まり結晶化し易くなり、溶融時のせん断発熱量が高くなりAV値の増加、極限粘度の低下があり、20当量/トンを超えると、耐加水分解性が低下してしまう。
ポリエステル原料樹脂Aのカルボキシル基量は5~15当量/トンであることが好ましく、8~15当量/トンであることがさらに好ましい。なお、本明細書中において、「当量/トン(eq/t)」は1トンあたりのモル当量を表す。
ポリエステル原料樹脂Aの融点Tmは、250℃~265℃の範囲であることが好ましく、255℃~260℃の範囲であることがより好ましい。前記融点Tmは、5~20℃/minの昇温速度での示差走査熱量測定により求められる値である。
ポリエステル樹脂Aは、テレフタル酸を主たる成分とするジカルボン酸成分と、エチレングリコールを主たる成分とするジオール成分を縮重合することにより得ることができる。
ポリエステルを重合する際のエステル化反応において、触媒としてチタン(Ti)系化合物を用い、Ti添加量が元素換算値で、1ppm以上30ppm以下、より好ましくは2ppm以上20ppm以下、さらに好ましくは3ppm以上15ppm以下の範囲で重合を行なうことが好ましい。この場合、本発明のポリエステルフィルムには、1ppm以上30ppm以下のチタンが含まれる。
Ti系化合物の量が1ppm以上であると、重合速度が速くなり、好ましいIVが得られる。また、Ti系化合物の量が30ppm以下であると、COOHを上記の範囲を満足するように調節することが可能であり、また良好な色調が得られる。
また、ジオール成分として、脂肪族ジオールの少なくとも1種が用いられる場合が好ましい。脂肪族ジオールとして、エチレングリコールを含むことができ、好ましくはエチレングリコールを主成分として含有する。なお、主成分とは、ジオール成分に占めるエチレングリコールの割合が80質量%以上であることをいう。
また、前記PETとしては、ゲルマニウム(Ge)化合物、アンチモン(Sb)化合物、アルミニウム(Al)化合物、及びチタン(Ti)化合物から選ばれる1種又は2種以上を用いて重合されるPETが好ましく、より好ましくはTi化合物を用いたものである。
Ti系触媒の例としては、テトラ-n-プロピルチタネート、テトラ-i-プロピルチタネート、テトラ-n-ブチルチタネート、テトラ-n-ブチルチタネートテトラマー、テトラ-t-ブチルチタネート、テトラシクロヘキシルチタネート、テトラフェニルチタネート、テトラベンジルチタネート等のチタンアルコキシド、チタンアルコキシドの加水分解により得られるチタン酸化物、チタンアルコキシドと珪素アルコキシドもしくはジルコニウムアルコキシドとの混合物の加水分解により得られるチタン-珪素もしくはジルコニウム複合酸化物、酢酸チタン、蓚酸チタン、蓚酸チタンカリウム、蓚酸チタンナトリウム、チタン酸カリウム、チタン酸ナトリウム、チタン酸-水酸化アルミニウム混合物、塩化チタン、塩化チタン-塩化アルミニウム混合物、チタンアセチルアセトナート、有機酸を配位子とする有機キレートチタン錯体、等が挙げられる。
また、一般に、カルボキシル基量が多いほど耐加水分解性が悪化することが知られており、本発明の添加方法によってカルボキシル基量が少なくなることで、耐加水分解性の向上が期待される。
前記クエン酸キレートチタン錯体としては、例えば、ジョンソン・マッセイ社製のVERTEC AC-420など市販品として容易に入手可能である。
これにより、重合時の着色及びその後の溶融製膜時における着色が少なくなり、従来のアンチモン(Sb)触媒系のポリエステル樹脂に比べて黄色味が軽減され、また、透明性の比較的高いゲルマニウム触媒系のポリエステル樹脂に比べて遜色のない色調、透明性を持ち、しかも耐熱性に優れたポリエステル樹脂を提供できる。また、コバルト化合物や色素などの色調調整材を用いずに高い透明性を有し、黄色味の少ないポリエステル樹脂が得られる。
5価のリン化合物として、置換基として芳香環を有しない5価のリン酸エステルの少なくとも一種を用いることができる。本発明における5価のリン酸エステルとしては、例えば、リン酸トリメチル、リン酸トリエチル、リン酸トリ-n-ブチル、リン酸トリオクチル、リン酸トリス(トリエチレングリコール)、リン酸メチルアシッド、リン酸エチルアシッド、リン酸イソプロピルアシッド、リン酸モノブチル、リン酸ジブチル、リン酸ジオクチル、リン酸トリエチレングリコールアシッド等が挙げられる。
マグネシウム化合物を含めることにより、静電印加性が向上する。この場合に着色がおきやすいが、本発明においては、着色を抑え、優れた色調、耐熱性が得られる。
エステル化反応を一段階で行なう場合、エステル化反応温度は230~260℃が好ましく、240~250℃がより好ましい。
エステル化反応を多段階に分けて行なう場合、第一反応槽のエステル化反応の温度は230~260℃が好ましく、より好ましくは240~250℃であり、圧力は1.0~5.0kg/cm2が好ましく、より好ましくは2.0~3.0kg/cm2である。第二反応槽のエステル化反応の温度は230~260℃が好ましく、より好ましくは245~255℃であり、圧力は0.5~5.0kg/cm2、より好ましくは1.0~3.0kg/cm2である。さらに3段階以上に分けて実施する場合は、中間段階のエステル化反応の条件は、前記第一反応槽と最終反応槽の間の条件に設定するのが好ましい。
重縮合は、エステル化反応で生成されたエステル化反応生成物を重縮合反応させて重縮合物を生成する。重縮合反応は、1段階で行なってもよいし、多段階に分けて行なうようにしてもよい。
このような積層ポリエステルフィルムに、カルボン酸基と水酸基との合計が3以上である構成成分(以下、「≧3官能成分」と記す場合がある。)、あるいは、イソシアネート化合物、カルボジイミド化合物、又はエポキシ化合物の少なくとも1種類の末端封止剤を含むことが好ましい。これらの「≧3官能成分」、「末端封止剤」は単独で使用しても良く、組合せて使用しても良い。
ポリエステルフィルム中の≧3官能成分が存在することで、重縮合に使用されなかった官能基が、塗布層中の成分と水素結合、共有結合することでより密着を向上させることができる。このような効果は≧3官能成分を本発明の結晶化度分布を持つポリエステルフィルム基材と併用することで、相乗効果が得られる。即ち結晶化度の低いところに貫入した塗布層の素材が、上記官能基と結合を形成し密着力を向上するためである。この時、貫入することで表面のみでの反応に比べ、より一層上記官能基と反応する数が増え密着力が増加し易い。このため≧3官能成分(p)の量が0.005モル%以上であれば、密着力がさらに向上し易い。一方、≧3官能成分(p)の量が2.5モル%以下であれば、ポリエステル中で結晶形成し、強度が低下し難く、その結果凝集破壊を発現し難く、密着力を向上させることができる。
本発明におけるポリエステルは、末端封止剤、光安定化剤、酸化防止剤などの添加剤を更に含有することができる。
そのため、特に好ましくは単官能性の末端封止剤を用いることであり、特に単官能性のエポキシ化合物が好ましい。
これらの紫外線吸収剤のうち、繰り返し紫外線吸収に対する耐性が高いという点で、トリアジン系紫外線吸収剤がより好ましい。なお、これらの紫外線吸収剤は、上述の紫外線吸収剤単体でフィルムに添加してもよいし、有機系導電性材料や、非水溶性樹脂に紫外線吸収剤能を有するモノマーを共重合させた形態で導入してもよい。
リサイクル材Bとしては、ポリエステルの粉砕物、回収ポリエステルを再溶融したリサイクル材などが挙げられる。コア層を形成する原料樹脂として、ポリエステルA2のほか、極限粘度(IV)が0.55~0.80であり、カルボキシル基量(AV)が35当量/トン以下であるリサイクル材Bを10~40質量%含む混合原料樹脂を用いることで、押出機内で溶融する際、溶融粘度差を低下させ、せん断発熱量を小さくすることができ、溶融温度が小さくなり、溶融粘度を調整し易くできるとともに、製造コストの上昇を抑制することができる。
混合原料樹脂全量に対するリサイクル材Bの含有量は、積層フィルム全体の耐加水分解性の観点から、15~40質量%であることが好ましく、20~40質量%であることがより好ましい。
コア層の形成に用いるリサイクル材Bは、IVが0.55未満では配合されて積層フィルムの力学物性を低下させ、0.80を超えると溶融押出時の溶融粘度を低下させる効果が小さくなり、せん断発熱量が大きくなって、熱分解を進めてAV値を増加させ、積層フィルムの耐加水分解性が低下する。
リサイクル材のIVは、0.60~0.80であることが好ましく、0.60~0.75であることがさらに好ましい。
ΔIVは、0.05~0.2であることがより好ましく、0.05~0.18であることがさらに好ましい。
コア層の形成に用いるリサイクル材Bは、AVが35当量/トンを超えると配合されたフィルムのAV値が大きく成り過ぎ耐加水分解性能が低下する。
リサイクル材BのAVは30当量/トン以下であることが好ましい。
また、リサイクル材Bの融点Tmは、255℃~260℃の範囲であることが好ましい。
次いで、準備した原料樹脂を以下の第1の乾燥工程と第2の乾燥工程によって乾燥させる。
前記ポリエステル原料樹脂A1を、100ppm以下の含水量に乾燥させる。
固相重合工程後のポリエステル原料樹脂A1を、例えば、露点温度-30℃の加熱窒素を用いて140~170℃で2~8時間乾燥させる。
原料樹脂の含水量は、カールフィッシャー水分計(京都電子工業(株)製、MKC-520)によって測定することができる。
前記ポリエステル原料樹脂A2及び前記リサイクル材Bを含み、ポリエステル樹脂の合計質量に対する前記リサイクル材Bの割合が15~40質量%である混合原料樹脂を、100ppm以下の含水量に乾燥させる。
例えば、露点温度-30℃の加熱窒素を用いて140~170℃で2~8時間乾燥させる。
前記第1の乾燥工程で乾燥された前記ポリエステル原料樹脂A1を溶融した第1の溶融樹脂と、前記第2の乾燥工程で乾燥された前記混合原料樹脂を溶融した第2の溶融樹脂とを、2台の押出機を用いてそれぞれ280~300℃の溶融樹脂温度になるように溶融し、一つのダイから共押出する。
図1に示す二軸押出機は、供給口12及び押出機出口14を有するシリンダー10(バレル)と、シリンダー10内で回転する2つのスクリュ20A,20Bと、シリンダー10の周囲に配置され、該シリンダー10内の温度を制御する温度制御手段30と、を備えている。供給口12の手前には原料供給装置46が設けられている。また、押出機出口14の先には、図2に示すようにギアポンプ44と、フィルタ42と、ダイ40が設けられている。
シリンダー10は原料樹脂を供給するための供給口12と、加熱溶融された樹脂が押し出される押出機出口14を有する。
シリンダー10の内壁面は、耐熱、耐磨耗性、及び腐食性に優れ、樹脂との摩擦が確保可能な素材を用いることが必要である。一般的には内面を窒化処理した窒化鋼が使用されているが、クロムモリブデン鋼、ニッケルクロムモリブデン鋼、ステンレス鋼を窒化処理して用いることもできる。特に耐摩耗性、耐食性を要求される用途では、遠心鋳造法によりニッケル、コバルト、クロム、タングステン等の耐腐食性、耐磨耗性素材合金をシリンダー10の内壁面にライニングさせたバイメタリックシリンダーを用いることや、セラミックの溶射皮膜を形成させることが有効である。
ベント16A,16Bは脱気効率との関係で、開口面積やベントの数を適正にすることが求められる。本発明で用いる二軸押出機100は、1箇所以上のベント16A,16Bを有することが望ましい。なお、ベント16A,16Bの数が多過ぎると、溶融樹脂がベントから溢れ出るおそれ、滞留劣化異物増加の懸念があるので、ベントは1箇所又は2箇所設けることが好ましい。
また、ベント付近の壁面に滞留した樹脂や析出した揮発成分が押出機100(シリンダー10)の内部に落下すると、製品に異物として顕在化する可能性があり、注意が必要である。滞留については、ベント蓋の形状の適正化や、上部ベント、側面ベントの適正な選定が有効であり、揮発成分の析出は、配管等の加熱で析出を防止する手法が一般的に用いられる。
例えば、樹脂供給口12を真空化したり、窒素パージを行うことで酸化分解を抑えることができる。
また、ベント16A,16Bを複数箇所に設けることで、原料水分量が2000ppm程度の場合でも、50ppm以下に乾燥した樹脂を単軸で押出した場合と同様の押出しが可能である。
剪断発熱による樹脂分解を抑えるため、押出と脱気が両立できる範囲でニーディング等のセグメントは極力設けないことが好ましい。
また、スクリュ出口(押出機出口)14の圧力が大きいほど剪断発熱が大きくなるため、ベント16A,16Bによる脱気効率と押出の安定性が確保できる範囲内で、押出機出口14の圧力は極力低くすることが好ましい。
シリンダー10内には、モータおよびギアを含む駆動手段21によって回転する2つのスクリュ20A,20Bが設けられている。スクリュ径Dが大きくなるほど、大量生産が可能である一方、溶融ムラが生じ易い。スクリュ径Dは、30~250mm以下が好ましく、より好ましくは50~200mm以下である。
2つのスクリュ20A,20Bの回転方向もそれぞれ同方向と異方向に分かれる。異方向回転スクリュ20A,20Bは同方向回転型よりも混練効果が高く、同方向回転型は自己清掃効果を持っているため、押出機内の滞留防止には有効である。
さらに軸方向も平行と斜交があり、強いせん断を付与する場合に用いられるコニカルタイプの形状もある。
加熱溶融部に、ニーディングディスクやローターなどの剪断を付与するセグメントを用いることで、原料樹脂をより確実に溶融することができる。また、逆スクリュやシールリングを用いることにより、樹脂をせき止め、ベント16A,16Bを引く際のメルトシールを形成することができる。例えば、図1に示すように、ベント16A,16B付近に、上記のような原料樹脂の溶融を促進する混練部24A,24Bを設けることができる。
シリンダー10の周囲には、温度制御手段30が設けられている。図1に示す押出機100では、原料供給口12から押出機出口14に向けて長手方向に9つに分割された加熱/冷却装置C1~C9が温度制御手段30を構成している。このようにシリンダー10の周囲に分割して配置された加熱/冷却装置C1~C9によって、例えば加熱溶融部C1~C7と冷却部C8,C9の各領域(ゾーン)に区画し、シリンダー10内を領域ごとに所望の温度に制御することができる。
シリンダー10の押出機出口14には、押出機出口14から押出された溶融樹脂をフィルム状(帯状)に吐出するためのダイ40が設けられている。また、シリンダー10の押出機出口14とダイ40との間には、フィルムに未溶融樹脂や異物が混入することを防ぐためのフィルタ42が設けられている。
厚み精度を向上させるためには、押出量の変動を極力減少させることが重要である。押出量の変動を極力減少させるために押出機100とダイ40との間にギアポンプ44を設けてもよい。ギアポンプ44から一定量の樹脂を供給することにより、厚み精度を向上させることができる。特に、二軸スクリュ押出機を用いる場合には、押出機自身の昇圧能力が低いため、ギアポンプ44による押出安定化を図ることが好ましい。
シリンダー内に供給された原料樹脂は融点Tm(℃)以上の温度に加熱されるが、樹脂温度が低過ぎると溶融押出時の溶融が不足し、ダイ40からの吐出が困難になるおそれがあり、樹脂温度が高過ぎると熱分解によってCOOHが著しく増加して耐加水分解性の低下を招くおそれがある。
ここで、溶融樹脂温度とは、Tダイから押出された溶融樹脂を接触式温度計によって測定される温度を意味する。
溶融樹脂温度が280℃未満であると、溶融樹脂の一部が固化して未溶融樹脂が発生し、300℃を超えると、熱分解によりCOOHが増大して耐加水分解性が低下し易くなる。
熱分解によるCOOHの発生をより抑制できる点で、押出し機内を窒素置換して行なうことがより好ましい。
コア層を形成するためのリサイクル材Bとポリエステル原料樹脂A2との混合原料樹脂を溶融した第2の溶融樹脂の溶融樹脂温度は、280~300℃であることが好ましく、280~290℃であることがより好ましい。
スキン層とコア層を合流させてTダイより押出し際の垂れ幕の溶融樹脂温度は、280~300℃であることが好ましく、280~295℃であることがより好ましい
溶融押出された前記第1の溶融樹脂及び前記第2の溶融樹脂を、前記第2の溶融樹脂の膜の厚みが前記第1の溶融樹脂の膜の厚みよりも厚く、かつ、前記第1の溶融樹脂の膜が前記第2の溶融樹脂の膜の少なくとも一方の面に積層した状態でキャストロール上で冷却固化し、少なくとも2層からなる積層体を成形する。
キャストロールの温度は、10℃以上80℃以下が好ましく、より好ましくは15℃以上70℃以下、さらに好ましくは20℃以上60℃以下である。さらに、メルトとキャストロールとの間で密着性を高め、冷却効率を上げる観点からは、キャストロールにメルトが接触する前に静電気を印加しておくことが好ましい。さらに、キャストロール反対面から冷風を当てたり、冷却ロールを接触させ、冷却を促すことも好ましい。これにより、厚手のフィルムであっても、効果的に冷却が行なえる。
第1の溶融樹脂膜と第2の溶融樹脂膜の厚み比は、1/150~1/4であることが好ましく、1/100~1/8であることがより好ましい。
ポリエステル原料樹脂Aを使っており、AV値が小さく結晶化し易い第1の溶融樹脂膜の厚みを薄くすることで、押出されたメルトがガラス転移温度(Tg)以下に冷却するまでの所要時間を短くすることができる。その結果、スキン層の結晶化が抑制され積層フィルムの透明性が向上する。なお、Tgはガラス転移温度を表し、JIS K7121或いはASTM D3418-82等に基づいて測定することができる。
成形工程により作製された積層体(未延伸の積層ポリエステルフィルム)を長手方向(MD)及び幅方向(TD)にそれぞれ延伸して二軸延伸(縦延伸及び横延伸)を行う。
また、積層ポリエステルフィルムの強度を向上させる目的で、多段縦延伸、再縦延伸、再縦横延伸、横・縦延伸など公知の延伸フィルムに用いられる延伸を行ってもよい。縦延伸と横延伸の順序を逆にしてもよい。
-熱固定工程-
得られた二軸延伸フィルムの結晶配向を完了させて、平面性と寸法安定性を付与するために、引き続きテンター内にて、二軸延伸フィルムの熱固定処理を行い、均一に徐冷後、室温まで冷却する。一般に、熱固定処理温度(Ts)が低いとフィルムの熱収縮が大きいため、高い熱寸法安定性を付与するためには、熱処理温度は高い方が好ましい。しかしながら、熱処理温度を高くし過ぎると配向結晶性が低下し、その結果形成されたフィルムが耐加水分解性に劣ることがある。
本発明では、二軸延伸フィルムの熱固定処理を行う際、150~250℃とすることが好ましく、180~230℃とすることがより好ましい。
また必要に応じて、幅方向あるいは長手方向に1~12%の緩和(弛緩)処理を施してもよい。
熱固定されたポリエステルフィルムは通常Tg以下まで冷却され、ポリエステルフィルム両端のクリップ把持部分をカットしロール状に巻き取られる。この際、最終熱固定処理温度以下、Tg以上の温度範囲内で、幅方向及び/または長手方向に1~12%弛緩処理することが好ましい。
また、冷却は、最終熱固定温度から室温までを毎秒1℃以上100℃以下の冷却速度で徐冷することが寸法安定性の点で好ましい。特に、Tg+50℃からTgまでを、毎秒1℃以上100℃以下の冷却速度で徐冷することが好ましい。冷却、弛緩処理する手段は特
に限定はないが、特に複数の温度領域で順次冷却しながら、これらの処理を行うことが、ポリエステルフィルムの寸法安定性向上の点で好ましい。
上記のような工程を経て、本発明では、極限粘度が0.55~0.80であり、カルボキシル基量が7~25当量/トンである第1のポリエステル層(スキン層)、及び全質量に対して10~40質量%のポリエステル樹脂のリサイクル材を含んで形成され、極限粘度が0.55~0.76であり、カルボキシル基量が8~30当量/トンであると共に、前記第1のポリエステル層の厚みより厚い第2のポリエステル層(コア層)を含む積層構造を有し、極限粘度が0.55以上であってカルボキシル基量が30当量/トン以下であるポリエステルからなる二軸配向した積層ポリエステルフィルムを製造することができる。
本発明により製造される積層ポリエステルフィルムは、電気絶縁性に優れるほか、厚みムラが小さく、高温高湿度下での耐加水分解性が優れているため、電気電子部材に好適であり、特に、太陽電池部材用ポリエステルフィルム、具体的には、太陽電池発電モジュールの太陽光入射側とは反対側の裏面に配置される裏面保護シート(いわゆる太陽電池用バックシート)、バリアフィルム基材等の用途に好適である。
太陽電池素子の例としては、単結晶シリコン、多結晶シリコン、アモルファスシリコンなどのシリコン系、銅-インジウム-ガリウム-セレン、銅-インジウム-セレン、カドミウム-テルル、ガリウム-砒素などのIII-V族やII-VI族化合物半導体系など、各種公知の太陽電池素子を適用することができる。
‐二軸押出機‐
押出機として、図1に示すように2箇所にベントが設けられたシリンダー内に下記構成のスクリュを備え、シリンダーの周囲には長手方向に9つのゾーンに分割して温度制御を行うことができるヒータ(温度制御手段)を備えたダブルベント式同方向回転噛合型の二軸押出機を準備した。
スクリュ径D:65mm
長さL[mm]/スクリュ径D[mm]:31.5(1ゾーンの幅:3.5D)
スクリュ形状:第1ベント直前に可塑化混練部、第2ベント直前に脱気促進混練部
ギアポンプ:2ギアタイプ
フィルタ:金属繊維焼結フィルタ(孔径20μm)
ダイ:リップ間隔4mm
ポリエステル樹脂Aとしては、触媒としてTi-クエン酸錯体を用いて製造したポリエチレンテレフタレート(極限粘度IV:0.8dl/g、COOH量AV:13eq/t、乾燥後の含水率:45ppm)のペレット(PET1)を用意した。
リサイクル材Bとしては、ポリエチレンテレフタレート(極限粘度IV:0.76dl/g、COOH量AV:15eq/t、乾燥後の含水率:48ppm)のリサイクルチップ1を用意した。
コア層の形成にはPET1及びリサイクルチップ1を「PET1:リサイクルチップ1=80:20」の比率(質量比)で混合した材料を、スキン層の形成にはPET1をそれぞれ用いて共押出しにより積層体(未延伸フィルム)を形成した。
各押出機のバレル設定温度を280℃に、スクリュの回転数を80rpmにそれぞれ設定した。供給口から各原料を供給して加熱溶融し溶融押出を行った。Tダイから押出された溶融樹脂温度は291℃であった。
なお、ダイ出口から冷却ロールまでの搬送域(エアギャップ)は、この搬送域を囲い、この中に調湿空気を導入することにより、湿度を30%RHに調節してある。押出機の押出量及びダイのスリット幅の調整により、メルト厚みを平均で約3300μmとした。
次いで、得られた未延伸フィルムの二軸延伸を行った。延伸倍率は、縦延伸:3倍、横延伸:4.2倍とした。これにより、厚さ250μmの積層PETフィルムを得た。
製造したPETフィルムについて以下の方法により評価を行い、結果を表1に示した。
極限粘度(IV)は、溶液粘度(η)と溶媒粘度(η0)の比ηr(=η/η0;相対粘度)から1を引いた比粘度(ηsp=ηr-1)を濃度で割った値を濃度がゼロの状態に外挿した値である。IVは、ウベローデ型粘度計を用い、ポリエステル樹脂を1,1,2,2-テトラクロルエタン/フェノール(=2/3[質量比])混合溶媒に溶解させ、25℃の溶液粘度から求めた。
0.1gの試料をベンジルアルコール10mlに溶解後、さらにクロロホルムを加えて混合溶液を得、これにフェノールレッド指示薬を滴下した。この溶液を、基準液(0.01N KOH-ベンジルアルコール混合溶液)で滴定し、フェノールレッド指示薬の色が黄色から赤色に変わる直前の基準液の滴下量からカルボキシル基量を求めた。
原料のPETペレット、リサイクルチップ、得られたPETフィルムについては、0.1gの試料をベンジルアルコール10mlに溶解後、さらにクロロホルムを加えて混合溶液を得、これにフェノールレッド指示薬を滴下した。この溶液を、基準液(0.01N KOH-ベンジルアルコール混合溶液)で滴定し、フェノールレッド指示薬の色が黄色から赤色に変わる直前の基準液の滴下量からカルボキシル基量を求めた。
120℃×100%RH条件で湿熱処理(サーモ処理)をした際、処理前後での引張破断伸度保持率が50%となった時間が100時間未満の場合を×、100時間以上の場合を○、120時間を越えた場合を◎とした。引張試験はJIS K 7127に則った。
ここで「伸度保持率(Lr)」とは、湿熱経時前の破断伸度(Li)と、湿熱経時後の破断伸度(Lt)の比率(%)を指し、下記式で求められた値である。
Lr(%)=100×(Lt)/(Li)
ヘイズの測定は、JIS K 7136に則った。2%未満であれば◎、2%以上3%未満であれば○、3%以上であれば×とした。
厚み250μmサンプルをカラーメーター(ND-101D(日本電色工業(株)製))で測定し、フィルムb値が2を超える場合は×、1を超え2以下であれば○、1以下であれば◎。
フィルム断面をかみそりで切断し、光学顕微鏡を使って観察した。表層の厚みムラが30%以上変化した場合は×、20%を越え、30%未満であれば○、20%未満であれば◎。
5m長×1m幅のフィルムを目視で確認した際、スジ状の5mm以上の連続ムラが確認できれば×、5mm以下の部分ムラが確認できるだけであれば○、全く確認できなければ◎。
原料及び押出し条件を表1に示すように変更したこと以外は実施例1と同様にしてポリエステルフィルムを製造して評価を行った。なお、表1中、「触媒1」はTi-クエン酸錯体(ジョンソン・マッセイ社製、VERTEC AC-420)、「触媒2」はTiO2(住友金属工業社製)である。また、実施例14、15では、末端封止剤として、カルボジイミド系化合物:ラインケミー社製「タバクゾールP100」、エポキシ系化合物:Hexion Speciality Chemicals社製「カージュラE10P」をそれぞれ使用し、樹脂原料と一緒に押出機に添加して配合した。
原料及び押出し条件を表2に示すように変更したこと以外は実施例1と同様にしてポリエステルフィルムを製造して評価を行った。
コア層の形成にリサイクルチップ用いていない比較例1では、押出工程におけるせん断発熱が大きく溶融樹脂温度が300℃を超え、IVの低下とAVの上昇が大きかった。その結果、耐加水分解性能が低下する。
本明細書に記述された全ての刊行物や特許出願、並びに技術標準は、それら個々の刊行物や特許出願、並びに技術標準が引用文献として特別に、そして個々に組み込むことが指定されている場合には、該引用文献と同じ限定範囲においてここに組み込まれるものである。上記本発明の好ましい実施態様の詳細は、当業者がその適用を企図する態様により様々な応用形態に自在に変更できることは言うまでも無いことである。本発明の範囲は下記特許請求の範囲及びその等価物に拠って決定されることを企図するものである。
Claims (10)
- 極限粘度が0.60~0.85であり、カルボキシル基量が5~20当量/トンであるポリエステル原料樹脂A1及びA2とからなるポリエステル原料樹脂Aと、極限粘度が0.55~0.80であり、カルボキシル基量が35当量/トン以下であるポリエステル樹脂のリサイクル材Bを準備する原料準備工程と、
前記ポリエステル原料樹脂A1を、100ppm以下の含水量に乾燥させる第1の乾燥工程と、
前記ポリエステル原料樹脂A2及び前記リサイクル材Bを含み、ポリエステル樹脂の合計質量に対する前記リサイクル材Bの割合が10~40質量%である混合原料樹脂を、100ppm以下の含水量に乾燥させる第2の乾燥工程と、
前記第1の乾燥工程で乾燥された前記ポリエステル原料樹脂A1を溶融した第1の溶融樹脂と、前記第2の乾燥工程で乾燥された前記混合原料樹脂を溶融した第2の溶融樹脂とを共押出する際、それぞれTダイから押出された溶融樹脂温度が280~300℃となる溶融押出工程と、
溶融押出された前記第1の溶融樹脂及び前記第2の溶融樹脂を、前記第2の溶融樹脂の膜の厚みが前記第1の溶融樹脂の膜よりも厚く、かつ、前記第1の溶融樹脂の膜が前記第2の溶融樹脂の膜の少なくとも一方の面に積層した状態でキャストロール上で冷却固化し、少なくとも2層からなる積層体を成形する成形工程と、
前記積層体を長手方向及び幅方向に延伸する二軸延伸工程と、
を有する積層ポリエステルフィルムの製造方法。 - 前記ポリエステル原料樹脂A及び前記リサイクル材Bの少なくとも一方は、チタン化合物を重合触媒として合成されたポリエステル樹脂である請求項1に記載の積層ポリエステルフィルムの製造方法。
- 前記チタン化合物が少なくとも一種の有機酸を配位子とする有機キレートチタン錯体を含む請求項2に記載の積層ポリエステルフィルムの製造方法。
- 前記溶融押出工程において、前記第1溶融樹脂及び前記第2溶融樹脂の少なくとも一方に、エポキシ化合物又はカルボジイミド化合物から選ばれる少なくとも1種の末端封止剤を積層ポリエステルフィルム全質量に対して0.1質量%以上5質量%以下配合する請求項1~請求項3のいずれか一項に記載の積層ポリエステルフィルムの製造方法。
- 前記成形工程は、溶融押出された前記第2の溶融樹脂の膜を、溶融押出された前記第1の溶融樹脂の膜で挟んだ積層状態でキャストロール上で冷却固化し、3層からなる積層構造の積層体を成形する請求項1~請求項4のいずれか一項に記載の積層ポリエステルフィルムの製造方法。
- 示差走査熱量測定による前記ポリエステル原料樹脂Aの融点Tmが、250℃~265℃の範囲である請求項1~請求項5のいずれか一項に記載の積層ポリエステルフィルムの製造方法。
- 極限粘度が0.55~0.80であり、カルボキシル基量が7~25当量/トンであるポリエステルからなる第1のポリエステル層、及び
全質量に対して10~40質量%のポリエステル樹脂のリサイクル材を含んで形成され、極限粘度が0.55~0.76であり、カルボキシル基量が8~30当量/トンであるポリエステルからなると共に、前記第1のポリエステル層の厚みより厚い第2のポリエステル層
を含む積層構造を有し、
請求項1~請求項6のいずれか1項に記載のポリエステルフィルムの製造方法により作製された、極限粘度が0.55以上であってカルボキシル基量が30当量/トン以下であるポリエステルからなる積層ポリエステルフィルム。 - 前記積層構造は、前記第2のポリエステル層と、前記第2のポリエステル層を挟む2層の前記第1のポリエステル層とを含む3層構造である請求項7に記載の積層ポリエステルフィルム。
- 請求項7又は請求項8に記載された積層ポリエステルフィルムを備えた太陽電池用バックシート。
- 請求項9に記載された太陽電池用バックシートを備えた太陽電池モジュール。
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