JP2010158828A - Polyester film for solar cell back protecting film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester film for a solar cell back protecting film which is excellent in durability and adhesive properties at a high temperature and in high humidity in a thin film silicon solar cell. <P>SOLUTION: The polyester film for the solar cell back protecting film has a covering layer which has a whiteness degree of at least 50, contains 3-50 mass% of fine particles 0.1-3 μm in average particle size, has a film acid value of 1-30 (eq/ton), and contains at least one of a polyester resin, a polyurethane resin, or a polyacrylic resin as a main component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyester film for a solar cell back surface protective film.

  The demand for solar cells capable of obtaining electric power by using energy not derived from petroleum fuel is increasing from the viewpoint of environmental protection. As described in, for example, Japanese Utility Model Publication No. Hei 6-38264, a solar cell module generally sandwiches a plurality of plate-like solar cell elements between a glass substrate on the light receiving side and a back surface protective film, A structure in which an internal gap is filled with a sealing resin such as an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA resin) is employed.

  A plastic film having excellent mechanical properties, heat resistance, and moisture resistance is used for the back surface protective film. For example, Japanese Patent Application Laid-Open Nos. 2002-26354 and 2003-60218 propose a back surface protective film using a polyethylene terephthalate film. And a white back surface protective film may be used for the purpose of improving the power generation efficiency of a solar cell.

JP 2002-26354 A JP 2003-60218 A JP-A-60-250946 JP 2004-247390 A JP 2002-134771 A JP 2007-208179 A JP 2008-85270 A

  By using a white polyester film, it is possible to reflect sunlight and increase power generation efficiency. A white polyester film needs to add a large amount of particles to a polyester substrate. Therefore, in order to improve their dispersibility and mixing state, the raw material is preliminarily mixed with two or more kinds of materials, and the resin is deteriorated because the melting time is increased even in a normal extrusion process. Easy to do. Therefore, when used as a solar cell under high temperature and high humidity, it has been a problem that durability is poor. Furthermore, when using them as a solar cell module, it is necessary to have adhesiveness with EVA resin.

  The present invention relates to the above-mentioned problem, that is, a polyester film for a solar cell back surface protective film having good durability under high temperature and high humidity and good adhesion to EVA resin.

  The present invention contains 3 to 50% by weight of fine particles having a whiteness of 50 or more and an average particle diameter of 0.1 to 3 μm, and the acid value of the film is 1 (eq / ton) to 30 (eq / ton). It is a polyester film for solar cell back surface protective films characterized by having a coating layer which has at least one kind of polyester resin, polyurethane resin or polyacrylic resin as a main component.

  The present invention has light reflection efficiency, excellent durability under high temperature and high humidity, and good adhesiveness with EVA resin. Therefore, it is useful in solar cells, particularly thin film silicon solar cells.

  The polyester in the present invention is a polycondensation of an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid or an ester thereof with a glycol such as ethylene glycol, diethylene glycol, 1,4-butanediol or neopentyl glycol. Polyester produced. In addition to the method of directly reacting aromatic dicarboxylic acid and glycol, these polyesters can be polycondensed by transesterification of alkyl ester of aromatic dicarboxylic acid and glycol, or diglycol ester of aromatic dicarboxylic acid. Can be produced by a method such as polycondensation. Typical examples of such polyester include polyethylene terephthalate, polyethylene butylene terephthalate, polyethylene-2, 6-naphthalate and the like. This polyester may be a homopolymer or a copolymer of a third component. In any case, in the present invention, a polyester having an ethylene terephthalate unit, a butylene terephthalate unit or an ethylene-2,6-naphthalate unit of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more is preferable. .

  The polyester used as the film raw material preferably has an acid value of 1 (eq / ton) to 30 (eq / ton), more preferably 2 (eq / ton) to 20 (eq / ton), Preferably they are 2 (eq / ton) or more and 16 (eq / ton) or less. If it exceeds 30 (eq / ton), a film having good hydrolysis resistance cannot be obtained. Polyesters of less than 1 (eq / ton) are difficult to produce industrially.

  The film of the present invention contains fine particles having an average particle size of 0.1 to 3 μm in an amount of 3 to 50% by mass, preferably 4 to 25% by mass, based on the total mass of the film. If it is 0.1 μm or less or exceeds 3 μm, it is difficult to make the whiteness of the film 50 or more even if the addition amount is increased. Moreover, if it is less than 3 mass%, it will become difficult to make whiteness into 50 or more. If it exceeds 50% by mass, the film weight increases, making it difficult to handle it during processing.

In addition, the average particle diameter of this invention is calculated | required by the electron microscope method. Specifically, the following method is used.
The fine particles are observed with a scanning electron microscope, the magnification is appropriately changed according to the size of the particles, and the photographed image is enlarged and copied. Next, the outer circumference of each particle is traced for at least 200 fine particles selected at random. The equivalent circle diameter of the particles is measured from these trace images with an image analysis apparatus, and the average value of these is taken as the average particle diameter.

  As the fine particles of the present invention, inorganic or organic particles can be used. Examples of these fine particles include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, barium sulfate, carbon black, acid value zinc, titanium oxide, zinc sulfide, and organic white pigment, but are not particularly limited. Absent. From the viewpoint of improving whiteness and productivity, titanium oxide or barium sulfate is preferable, and titanium oxide is more preferable. The titanium oxide may be either anatase type or rutile type. Further, the surface of the fine particles may be subjected to an inorganic treatment such as alumina or silica, or may be subjected to an organic treatment such as silicon or alcohol.

  Fine particles can be added to the film by using a known method, but a master batch method (MB method) in which a polyester resin and fine particles are mixed in an extruder in advance is preferable. Further, it is possible to adopt a method in which a polyester resin and fine particles which have not been dried in advance are put into an extruder and MB is produced while moisture and air are deaerated. Furthermore, it is preferable to prepare an MB using a polyester resin that has been slightly dried in advance to suppress an increase in the acid value of the polyester. In this case, a method of extruding while degassing, a method of extruding without deaeration with a sufficiently dried polyester resin, and the like can be mentioned.

  The film of the present invention may contain many fine cavities inside. In that case, the apparent specific gravity is 0.7 or more and 1.3 or less, preferably 0.9 or more and 1.3 or less, more preferably 1.05 or more and 1.2 or less. If it is less than 0.7, the film is not elastic and processing at the time of producing the solar cell module becomes difficult. Even if the film exceeds 1.3, it is within the range of the film of the present invention. However, if the film exceeds 1.3, the film weight is so large that it may become an obstacle when considering the reduction in weight of solar cells. There is.

  The fine cavities can be formed from a thermoplastic resin that is incompatible with the fine particles and / or polyester described below. The term “cavity derived from a thermoplastic resin that is incompatible with fine particles or polyester” means that there are voids around the fine particles or the thermoplastic resin. For example, confirm with a cross-sectional photograph of the film by an electron microscope. Can do.

  The polyester used in the present invention may be optionally added with an incompatible thermoplastic resin, and is not particularly limited as long as it is incompatible with the polyester. Specific examples include polystyrene resins, polyolefin resins, polyacrylic resins, polycarbonate resins, polysulfone resins, and cellulose resins. In particular, polystyrene resins or polyolefin resins such as polymethylpentene and polypropylene are preferably used.

  The mixing amount of these void forming agents, that is, the thermoplastic resin incompatible with the polyester, with respect to the polyester varies depending on the amount of the target void, but may be in the range of 3 to 20% by mass with respect to the entire film. More preferably, it is 5 to 18% by mass. And if it is less than 3 mass%, there exists a limit in increasing the production amount of a cavity. On the other hand, if it is 20% by mass or more, the stretchability of the film is remarkably impaired, and the heat resistance, strength, and waist strength are impaired.

  The polyester film for solar cell back surface protective film of the present invention can be a void-containing polyester film. The polyester film of the present invention may have a single layer or a laminated structure composed of two or more layers. The laminated structure includes a skin layer comprising a polyester layer containing many cavities derived from fine particles having an average particle size of 0.1 to 3 μm, and a polyester containing many cavities derived from a thermoplastic resin incompatible with polyester. It is also a preferred embodiment of the present invention to have a core layer composed of layers. Although the manufacturing method is arbitrary and is not particularly limited, for example, it can be manufactured as follows. First, as a method for joining the skin layer to the film surface, after supplying the polyester resin of the skin layer containing fine particles and the polyester resin of the core layer containing an incompatible thermoplastic resin to separate extruders, It is most preferable to employ a coextrusion method in which layers are laminated in a molten state and extruded from the same die.

  Each raw material is mixed, put into an extruder, melted, extruded from a T-die, and adhered to a cooling roll to obtain an unstretched sheet. The unstretched sheet is further expanded by stretching between rolls having a speed difference (roll stretching), stretching by gripping and expanding by a clip (tenter stretching), stretching by expanding with air pressure (inflation stretching), and the like. Axial orientation treatment. By performing the orientation treatment, interfacial peeling occurs between the polyester / incompatible thermoplastic resin and between the polyester / fine particles, and many fine cavities appear. Therefore, the conditions for stretching / orienting the unstretched sheet are closely related to the formation of cavities.

  First, the first-stage longitudinal stretching process is the most important process for forming many fine cavities in the film. In the longitudinal stretching, stretching is performed between two or many rolls having different peripheral speeds. As a heating means at this time, a method using a heating roll or a method using a non-contact heating method may be used, or they may be used in combination. Among these, the most preferable stretching method is a method using both roll heating and non-contact heating. In this case, first, the film is preheated to a temperature not higher than 50 ° C. to a glass transition point of polyester using a heating roll, and then heated with an infrared heater.

  Next, the uniaxially stretched film thus obtained is introduced into a tenter and stretched 2.5 to 5 times in the width direction. A preferable stretching temperature at this time is 100 ° C to 200 ° C. The biaxially stretched film thus obtained is subjected to heat treatment as necessary. The heat treatment is preferably performed in a tenter, and is preferably performed in the range of the melting point Tm-50 ° C. to Tm of the polyester.

  In this invention, in order to improve adhesiveness with EVA resin, it has a coating layer which has at least 1 type of a polyester resin, a polyurethane resin, or a polyacryl resin as a main component on the at least single side | surface of a polyester film. Here, the “main component” refers to a component that is 50% by mass or more of the solid components constituting the coating layer. The coating solution used for forming the coating layer of the present invention is preferably an aqueous coating solution containing at least one of water-soluble or water-dispersible copolymerized polyester resin, acrylic resin and polyurethane resin. Examples of these coating solutions include water-soluble or water-dispersible copolymerized polyester resin solutions, acrylic resin solutions, polyurethane resin solutions disclosed in Japanese Patent No. 3567927, Japanese Patent No. 3589232, Japanese Patent No. 3589233, and the like. Etc.

The coating layer can be obtained by applying the coating liquid on one or both sides of a uniaxially stretched film in the longitudinal direction, drying at 100 to 150 ° C., and further stretching in the transverse direction. The final coating amount of the coating layer is preferably controlled to 0.05 to 0.20 g / m ² . If the coating amount is less than 0.05 g / m ² , adhesion with the resulting EVA resin may be insufficient. On the other hand, when the coating amount exceeds 0.20 g / m ² , blocking resistance may be lowered. When coating layers are provided on both sides of the polyester film, the coating amounts of the coating layers on both sides may be the same or different, and can be independently set within the above range.

  It is preferable to add particles to the coating layer in order to provide easy slipping. It is preferable to use particles having an average particle size of 2 μm or less. When the average particle diameter of the particles exceeds 2 μm, the particles easily fall off from the coating layer. The particles to be included in the coating layer include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide, barium sulfate, calcium fluoride, and fluoride. Inorganic particles such as lithium, zeolite, molybdenum sulfide and mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate resin particles, benzoguanamine / formaldehyde condensate particles, melamine / formaldehyde condensate particles, polytetrafluoroethylene particles And heat resistant polymer particles. Among these particles, silica particles having a relatively close refractive index to the resin component of the coating layer are preferable.

  Moreover, a well-known method can be used as a method of apply | coating a coating liquid. For example, reverse roll coating method, gravure coating method, kiss coating method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, etc. can be mentioned. Or it can carry out in combination.

  Thus, the obtained film has a whiteness of 50 or more, preferably 60 or more. If it is less than 50, it is difficult to visually check the film when processing the solar cell module, and the processing efficiency is lowered.

  The film of the present invention has an acid value of 1 (eq / ton) to 30 (eq / ton), preferably 2 (eq / ton) to 20 (eq / ton), more preferably 2 (eq / ton). ton) to 16 (eq / ton). If it exceeds 30 (eq / ton), a film having good hydrolysis resistance cannot be obtained. A film of less than 1 (eq / ton) is difficult to produce industrially.

  The film of the present invention has a breaking elongation retention ratio of 60% or more, preferably 70% or more, more preferably 80% or more, which is an evaluation of hydrolysis resistance. If it is less than 60%, the durability as a solar cell back surface protective film is low and cannot be used.

Next, examples and comparative examples of the present invention will be shown. The measurement / evaluation method used in the present invention is shown below.
1) Apparent specific gravity A film is accurately cut into a 10 cm × 10 cm square, and its thickness is measured at 50 points to obtain an average thickness t (unit: μm). Next, the mass of the sample is measured to 0.1 mg and is set to w (unit: g). And the apparent specific gravity was calculated by the following formula.
Apparent specific gravity (−) = (w / t) × 10000

2) Whiteness Whiteness was carried out by using Nippon Denshoku Industries Co., Ltd. Z-1001DP according to the JIS-L1015-1981-B method.

3) Acid value It measured with the following method about the film and raw material polyester resin.

(1) Preparation of sample A film or a raw material polyester resin is pulverized and vacuum-dried at 70 ° C. for 24 hours, and then weighed in a range of 0.20 ± 0.0005 g using a balance. The mass at that time is defined as W (g). A sample weighed with 10 ml of benzyl alcohol is added to a test tube, the test tube is immersed in a benzyl alcohol bath heated to 205 ° C., and the sample is dissolved while stirring with a glass rod. Samples with dissolution times of 3 minutes, 5 minutes, and 7 minutes are designated as A, B, and C, respectively. Next, a new test tube is prepared, and only benzyl alcohol is added and processed in the same procedure, and the samples when the dissolution time is 3 minutes, 5 minutes, and 7 minutes are designated as a, b, and c, respectively.
(2) Titration Titration is performed using a 0.04 mol / l potassium hydroxide solution (ethanol solution) whose factor is known in advance. Phenol red is used as the indicator, and the titration (ml) of the potassium hydroxide solution is determined with the end point being changed from yellowish green to light red. The titration amounts of samples A, B, and C are XA, XB, and XC (ml). The titration amounts of samples a, b, and c are Xa, Xb, and Xc (ml).
(3) Calculation of acid value Using the titration amounts XA, XB, and XC for each dissolution time, the titration amount V (ml) at a dissolution time of 0 minutes is determined by the least square method. Similarly, titration volume V0 (ml) is obtained using Xa, Xb, and Xc. Subsequently, an acid value is calculated | required according to following Formula.

Formula 1

Ｗ：試料質量（ｇ）

W: Mass of sample (g)

4) Hydrolysis resistance HAST (Highly Accelerated Temperature and Humidity Stress Test) standardized in JIS-60068-2-66 was performed. The equipment was EHS-221 manufactured by ESPEC CORP. Under the conditions of 105 ° C., 100% Rh, 0.03 MPa.
The film was cut into 70 mm × 190 mm, and the film was placed using a jig. Each film was placed at a distance where it did not touch. The treatment was performed for 200 hours under the conditions of 105 ° C., 100% Rh, 0.03 MPa. Before and after the treatment, the elongation at break was measured according to JIS C 2318-1997 5.3.31 (tensile strength and elongation), and the elongation at break was calculated according to the following formula.

Formula 2

5) Two sheets of adhesive film with EVA resin cut to 20 mm width × 100 mm length, EVA resin sheet (SOLAR EVA (R) SC4 manufactured by High Sheet Industry Co., Ltd.) was cut to 20 mm width × 50 mm length I prepared one piece of each. The film was placed in the order of film / EVA resin sheet / film and pressed with a heat sealer so that the EVA resin sheet was positioned almost at the center of the film, and the surface to be evaluated for easy contact of the film was on the EVA side. . The pressure bonding conditions are 120 ° C. and 0.02 MPa for 5 minutes, then heated to 150 ° C., the press pressure is increased to 0.1 MPa, and the pressure is bonded for 25 minutes. Measure the adhesive strength of the thermocompression-bonded sample at 23 ° C and 50% RH in accordance with JIS-Z0237 with the unattached film sandwiched between the upper and lower clips at a peel angle of 180 ° and a tensile speed of 100 mm / min. did. EVA is an abbreviation for ethylene-vinyl acetate copolymer.
◎: 20 N / 20 mm or more: Very good adhesion ○: 10 N / 20 mm or more, less than 20 N / 20 mm ... Good adhesion Δ: 5 N / 20 mm or more and less than 10 N / 20 mm ... Adhesion slightly good × : Less than 5N / 20mm ... poor adhesion

Example 1
(Preparation of fine particle-containing masterbatch)
The average particle size was 50% by mass of polyethylene terephthalate resin (PET-I) having an intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton), which was previously dried at 120 ° C. and 10 ⁻³ torr for about 8 hours as a raw material. A mixture of 50% by mass of rutile titanium dioxide with a diameter of 0.3μm (electron microscopic method) is supplied to a vent type twin screw extruder, kneaded and extruded at 275 ° C while degassing to produce fine particles (titanium oxide) Containing masterbatch (MB-I) pellets were prepared. The acid value of this pellet was 8.6 (eq / ton).

(Preparation of coating solution)
A transesterification reaction and a polycondensation reaction are carried out by a conventional method, and as a dicarboxylic acid component (based on the whole dicarboxylic acid component) 46 mol% terephthalic acid, 46 mol% isophthalic acid and 8 mol% sodium 5-sulfonatoisophthalate, A water-dispersible sulfonic acid metal base-containing copolymer polyester resin having a composition of 50 mol% ethylene glycol and 50 mol% neopentyl glycol as a glycol component (based on the entire glycol component) was prepared. Next, 51.4 parts by mass of water, 38 parts by mass of isopropyl alcohol, 5 parts by mass of n-butyl cellosolve, 0.06 parts by mass of nonionic surfactant were mixed and then heated and stirred. After adding 5 parts by mass of a water-dispersible sulfonic acid metal base-containing copolymer polyester resin and continuing to stir until the resin is no longer agglomerated, the resin water dispersion is cooled to room temperature to obtain a solid content concentration of 5.0% by mass. A uniform water-dispersible copolymerized polyester resin liquid was obtained. Furthermore, after dispersing 3 parts by mass of aggregated silica particles (Silicia 310, manufactured by Fuji Silysia Co., Ltd.) in 50 parts by mass of water, 99.46 parts by mass of the water-dispersible copolyester resin liquid was mixed with 0.54 parts by mass of the aqueous dispersion was added, and 20 parts by mass of water was added with stirring to obtain a coating solution.

(Production of film)
Next, 50% by mass of polyethylene terephthalate resin (PET-I) and the raw material of the layer (A) in which 50% by mass of the previously prepared MB-I were mixed, 90% by mass of PET-I and MB-I 10% by mass is used as a raw material for the layer (B), put into separate extruders, mixed and melted at 280 ° C., and then, using a feed block, the layer B is joined to one side of the layer A in a molten state. . At this time, the discharge rate ratio of the A layer and the B layer was controlled using a gear pump. Subsequently, it was extruded onto a cooling drum adjusted to 30 ° C. using a T-die, and an unstretched sheet was prepared so as to be an A / B / A layer.

(Production of biaxially stretched film)
The obtained unstretched sheet was uniformly heated to 70 ° C. using a heating roll, and 3.3-fold roll stretching was performed at 90 ° C. to obtain a uniaxially stretched polyester film. The coating solution was applied to one side of the obtained uniaxially stretched polyester film so that the final coating layer thickness was 0.08 g / m ^2, and then dried at 135 ° C.

  By guiding the coated film to a tenter, heating it to 140 ° C. and transversely stretching it 3.7 times, fixing the width, applying heat treatment at 220 ° C. for 5 seconds, and further relaxing by 4% in the width direction at 220 ° C. A plastic film for a solar cell back surface protective film having a thickness of 188 μm (19/150/19) was obtained.

Example 2
(Preparation of cavity forming agent)
As raw materials, 20% by mass of polystyrene having a melt flow rate of 1.5 (manufactured by Nippon Polyste Co., Ltd., G797N), 20% by mass of vapor phase polymerization polypropylene having a melt flow rate of 3.0 (F300SP, manufactured by Idemitsu Petrochemical), and melt flow Rate 180 polymethylpentene (manufactured by Mitsui Chemicals: TPX DX-820) 60% by mass pellets were mixed, supplied to a twin screw extruder and kneaded sufficiently to prepare a cavity forming agent (MB-II).
A plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 1 except that PET-I: MB-I: MB-II was changed to 82: 10: 8 (mass%) as a raw material for the B layer. It was.

Example 3, Example 4, Comparative Example 1
In the same manner as in Example 2 except that the acid value of polyethylene terephthalate resin as a film raw material was 10.1, 19.5, 30.2 (respectively PET-II, PET-III, PET-IV). A plastic film for the battery back surface protective film was obtained.

Comparative Example 2
In the preparation of a master batch containing fine particles, a polyethylene terephthalate resin having an undried intrinsic viscosity of 0.64 and an acid value of 8.0 (eq / ton) stored in a paper bag as a raw material in a place where temperature and humidity are not controlled (PET-I) 50 mass% mixed with 50 mass% of rutile titanium dioxide having an average particle size of 0.3 μm (electron microscopic method) is supplied to a vent type twin screw extruder, kneaded and 305 ° C. A masterbatch (MB-III) pellet containing fine particles (titanium oxide) was prepared while degassing with a. The acid value of this pellet was 38.4 (eq / ton).
Other than that obtained the plastic film for solar cell back surface protective films by the method similar to Example 2. FIG.

Example 5
In the preparation of the fine particle-containing master batch, barium sulfate having an average particle size of 0.6 μm was used instead of rutile titanium dioxide (MB-IV), and it was used instead of MB-I as a raw material for the A layer. A plastic film for a solar cell back surface protective film was obtained in the same manner as in Example 2.

Comparative Example 3
A polyester film for a solar cell back surface protective film was obtained in the same manner as in Example 2 except that the coating layer was not provided.

  The polyester film for the solar cell back surface protective film of the present invention is excellent in durability under high temperature and high humidity, adhesiveness with EVA resin, and light reflection efficiency, and is useful as a material constituting the solar cell back surface protective film. is there.

Claims (4)

  3 to 50% by weight of fine particles having a whiteness of 50 or more and an average particle size of 0.1 to 3 μm, an acid value of the film of 1 (eq / ton) to 30 (eq / ton), polyester A polyester film for a solar cell back surface protective film, comprising a coating layer containing at least one of resin, polyurethane resin, or polyacrylic resin as a main component.   The apparent specific gravity of a film is 0.7 or more and 1.3 or less by having many fine cavities inside a film, The polyester film for solar cell back surface protective films of Claim 1 characterized by the above-mentioned.   Polyester layer (skin layer) containing many cavities derived from fine particles having an average particle size of 0.1 to 3 μm, and polyester layer (core layer) containing many cavities derived from a thermoplastic resin incompatible with polyester The polyester film for a solar cell back surface protective film according to claim 1 or 2, wherein the film is laminated.   The polyester film for a solar cell back surface protective film according to any one of claims 1 to 3, wherein an acid value of a polyester as a film raw material is 1 (eq / ton) or more and 30 (eq / ton) or less.