KR101776130B1 - White film for Solar Cell Module - Google Patents
White film for Solar Cell Module Download PDFInfo
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- KR101776130B1 KR101776130B1 KR1020110037131A KR20110037131A KR101776130B1 KR 101776130 B1 KR101776130 B1 KR 101776130B1 KR 1020110037131 A KR1020110037131 A KR 1020110037131A KR 20110037131 A KR20110037131 A KR 20110037131A KR 101776130 B1 KR101776130 B1 KR 101776130B1
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- resin
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- inorganic particles
- thermal conductivity
- white film
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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
Abstract
The present invention relates to a white film for a solar module. More specifically, the present invention relates to a white film for a solar module back sheet in which a matrix resin composed of a polyester resin and inorganic particles coated with a polymer resin are contained in the matrix resin.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a white film for a solar module back sheet, and relates to a new film which is replaced with a polyester film in a structure that is laminated with a conventional fluorine film / PET film / fluorine film.
Solar cells for solar power generation can start from silicon and various compounds, and become electricity when they become solar cells. However, since one cell does not have sufficient output, each cell must be connected in series or parallel. This state of connection is called a "solar module".
Solar modules are made up of glass, EVA (ethylene vinyl acetate, EVA), solar cell, EVA (ethylene vinyl acetate, EVA) and back sheet. The back sheet is stacked at the bottom of the module to protect the solar cell by blocking dust, impact and moisture. TPT (Tedlar / PET / Tedlar) type is widely used. Ribbon is used as current path Therefore, a material coated with silver or tin lead is used for copper.
Back sheet for photovoltaic module is the core material that protects cell by sticking to the back side of solar cell module. Durability, weather resistance, insulation, moisture barrier properties, etc. Generally, fluorine film and PET film are laminated.
Generally, the outer layer of the back sheet is made of a fluorine film excellent in weatherability and durability. Tedlar film made of PVF resin developed by DuPont in 1961 is mainly used. However, due to high price and shortage of supply, some companies substitute other film such as PET for use.
Eva (EVA) was jointly developed in 1970 by NASA and DuPont for materials for solar cells used in satellites. It is currently used as a standard for sealing materials for solar cells. Japanese companies (Mitsui Chemicals, Bridgestone) dominate over 70% of the world market. It serves to seal and fill the cell inside the solar cell. It is excellent in strength, transparency and insulation.
Polyethylene telephthalate (PET) film uses a flat film having a certain thickness and physical properties, and has excellent strength to form the basic structure of the back sheet. It has excellent physical, chemical, mechanical and optical properties and is widely used from food packaging materials and office supplies to semiconductor and display and other advanced electric and electronic products. In recent years, durability and weatherability are excellent, and the use thereof in solar cell back sheet is increasing.
Glass uses less iron to help prevent reflection of light.
BACKGROUND ART Conventionally, a TPT (Tedlar / PET / Tedlar) type backsheet requires a process of laminating a Tedlar film and a PET film through an adhesive agent, respectively. In addition, a back sheet and a sealing material, EVA A step of bonding with a polyurethane adhesive or the like was further required. The Tedlar film used for the conventional backsheet is expensive and occupies more than 80% of the manufacturing cost of the backsheet, which causes the cost of the backsheet to increase.
Therefore, studies have been made to develop the same effect as using a fluorine film without using a fluorine film which is high in price and low in supply and demand in order to lower the manufacturing cost.
An object of the present invention is to provide a white film for a solar cell module back sheet made of a polyester resin in order to solve the problem of a rise in price and inadequate supply and demand when a conventional fluororesin is used.
Another object of the present invention is to provide a white film having excellent weather resistance and excellent reflectivity for use as a solar cell module back sheet to increase light efficiency by returning light to a solar cell and excellent in hydrolysis resistance.
Another object of the present invention is to provide a white film excellent in processability while increasing the content of inorganic particles in order to satisfy an optical characteristic having a reflectance of at least 94% in a visible light region of 550 nm.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a white film for a solar module back sheet, which is a replacement of a conventional Tedlar film / PET film / Tedlar film by a polyester film alone. Or a white film for a solar cell module back sheet containing one or more layers of the white film of the present invention.
The inventors of the present invention have studied to replace a back sheet of a conventional polyethylene terephthalate (PET) film with a fluororesin film on both sides by a film made of a whole polyester resin. As a result, they have found that by blocking light and returning it to a solar cell, In order to satisfy such physical properties, it is necessary to include inorganic particles and it is possible to increase the reflectance by controlling the content of inorganic particles. However, when the content of inorganic particles is higher than the target reflectance It is found that the reflectance is high but unfortunately there is a problem in the process of producing the film.
Specifically, when the polyester film is produced, the polyester resin and the inorganic particles are generally mixed and melt-extruded in a temperature range similar to the melting temperature of the polyester resin, and then the melt Extruded and rapidly cooled in a casting roll at 20 to 30 ° C. to produce an uncrystallized unstretched sheet. In this case, when the inorganic particles are used in a quenching process in the casting roll, the heat transfer of the inorganic particles is too fast, There is a problem in the process that cracks are generated in the film due to the difference in crystallization progress speed of the surface.
The inventors of the present invention have found that when inorganic particles coated with a polymer resin having a heat transfer coefficient lower than that of a polyester matrix resin are used as a white film having high reflectance, The present inventors have found that a white film having a high reflectance can be produced by using a high content of particles with a maximum content of 30 wt%, and the processability of the film is improved.
More specifically, the present invention relates to
A matrix resin comprising a matrix resin and an inorganic particle coated with a polymer resin, wherein the matrix resin and the polymer resin coated on the inorganic particle have a thermal conductivity of the solar module back sheet ≪ / RTI >
[Formula 1]
Kp < Km - R int
(In the formula 1, Kp is of a polymeric resin coating on the inorganic particles, the thermal conductivity, Km is the thermal conductivity of the matrix resin R int is a thermal resistance of the interface between the polymer resin coating on the matrix resin and inorganic particles.)
Further, the present invention includes the back sheet of a solar module having one or more layers of the white film.
In addition, the solar module back sheet of the present invention may further include a metal deposition layer on one side or both sides of the white film.
Hereinafter, each configuration of the present invention will be described in more detail.
In the present invention, the matrix resin is a material forming the film, and in the present invention, a polyester resin is used.
The polyester resin is a generic term of a polymer in which a covalent bond between a monomer residue and a monomer residue, which is a main bond in the main chain, is an ester bond and is usually a dicarboxylic acid compound, a dihydroxy compound or a dicarboxylic acid ester derivative, And a condensation polymerization of a hydroxy compound.
Examples of the dicarboxylic acid compound include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5- Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid and phthalic acid, alicyclic dicarboxylic acids such as acetic acid, succinic acid, adipic acid, sebacic acid, dimeric acid, maleic acid and fumaric acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, And oxycarboxylic acids such as p-hydroxybenzoic acid and the like.
Examples of the dicarboxylic acid ester derivatives include esters of the above dicarboxylic acid compounds such as dimethyl terephthalate, diethyl terephthalate, terephthalic acid 2-hydroxyethyl methyl ester, 2,6-naphthalenedicarboxylic acid dimethyl, isophthalic acid Dimethyl, adipic acid dimethyl, maleic acid dimethyl, dimer acid dimethyl and the like.
Examples of the hydroxy compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Aliphatic hydroxy compounds such as hexanediol and neopentyl glycol, polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, And aromatic dihydroxy compounds such as a hydroxy compound, bisphenol A, and bisphenol S, and the like.
Of these, terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and the like can be preferably used as the dicarboxylic acid compound, and neopentyl glycol, ethylene glycol, 1,3-propanediol, 4-butanediol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, and the like can be preferably used.
In particular, it is preferable to use polyethylene terephthalate (PET) comprising terephthalic acid or dimethyl terephthalate and ethylene glycol.
The present invention may further comprise an additive as required in the matrix resin, and the additive preferably comprises at least one kind of inorganic particles and a UV stabilizer, an antioxidant, a heat stabilizer and the like. It may also contain a fluorescent whitening agent to improve the reflectance and whiteness of the film.
In the present invention, the inorganic particles reflect light passing through the solar cell and return it to the cell to increase the light efficiency, and block the UV transmitted through the PET film as a back sheet to suppress photolysis of PET. Concretely, for example, there may be mentioned titanium oxide (anatase type, rutile type), calcium carbonate, barium sulfate, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, magnesium oxide, calcium phosphate, silica, alumina, talc, It is preferable to use any one or two or more of them, more preferably titanium dioxide, and more preferably rutile type titanium dioxide, because the light absorption region shifts toward longer wavelength side, It is possible to suppress the photodegradation caused by the photocatalyst, thereby improving the durability. And the content thereof is preferably 10 to 30% by weight based on the entire white film content. When it is used in an amount of less than 10% by weight, it is difficult to apply the composition to a back sheet as a single layer film because of low reflectance, and when it is used in an amount exceeding 30% by weight, the sheet is brittle, So that the film-forming stability can be greatly reduced. Also, even if the film has a sufficient reflectance, the possibility of delamination on the surface of the film when used for a solar cell back sheet is increased, thereby deteriorating the quality of the back sheet.
The inorganic particles preferably have an average particle diameter of 0.1 to 5.0 mu m, particularly preferably 0.1 to 3.0 mu m. If the particle size is less than 0.1 탆, poor dispersibility due to the re-agglomeration of the fine particles occurs and the filters in the film-forming process are frequently clogged to drastically deteriorate the operability. When the particle size is more than 5.0 탆, the particle size becomes too large, There is a problem that the gloss is lowered due to an increase in surface unevenness.
In the present invention, it is preferable to use a resin having a lower thermal conductivity than that of a polyester resin which is a matrix resin, and more specifically, it is preferable to satisfy the following formula (1).
delete
[Formula 1]
Kp < Km - R int
(In the formula 1, Kp is of a polymeric resin coating on the inorganic particles, the thermal conductivity, Km is the thermal conductivity of the matrix resin R int is a thermal resistance of the interface between the polymer resin coating on the matrix resin and inorganic particles.)
In the present invention, when the temperature is outside the range of the above formula (1), heat transfer is fast due to the particles in the molten sheet, and the sheet breaks easily while passing through the cooling roll. However, A white film having excellent processability from cooling to stretching and having a high light reflectance can be produced. In the present invention, the polymer resin is not limited as far as the thermal conductivity of the polyester resin used as the matrix resin is a polymer resin that is smaller than the difference in heat transfer resistance between the mattress resin and the inorganic particle interface.
More specifically, for example, in the case where the polyester resin is a polyethylene terephthalate resin (thermal conductivity: 0.20 to 0.26), the polymer resin coated on the inorganic particles preferably has a glass transition temperature of 20 to 120 DEG C (Having a thermal conductivity of 0.18 to 0.22) or a polyester resin (having a thermal conductivity of 0.18 to 0.24).
The coating amount of the polymer resin is preferably 0.01 to 0.1% by weight based on the inorganic particle content, and is a resin having a glass transition temperature of 20 to 120 캜. When it is used in an amount less than 0.01% by weight, it is difficult to uniformly coat the inorganic particles and the heat transfer barrier property is poor. When the amount of the inorganic particles is more than 0.1% by weight, heat transfer is not transferred to the particles, Can occur.
Next, a method for producing a white film for a solar cell module back sheet of the present invention will be described in detail.
The white film of the present invention
a) mixing and melt-extruding a polyester resin and inorganic particles coated with a polymer resin satisfying Formula 1 below;
[Formula 1]
Kp < Km - R int
(In the formula 1, Kp is of a polymeric resin coating on the inorganic particles, the thermal conductivity, Km is the thermal conductivity of the matrix resin R int is a thermal resistance of the interface between the polymer resin coating on the matrix resin and inorganic particles.)
b) extruding the melt of step a) through a teide to produce an unoriented sheet in a cooling roll;
c) stretching the sheet longitudinally and transversely; And
d) fixing and relaxing the heat;
.
In the present invention, the melting temperature in the step a) is preferably melt-extruded near the melting point of the polyester resin, and preferably 280 to 290 ° C if the polyester resin is polyethylene terephthalate.
The inorganic particles coated with the polymer may be prepared by charging in a polymerization process and used for direct film formation, but also by compounding to prepare a master batch and injecting it into a film.
More specifically, the resin having a melting temperature of 285 DEG C is extruded through a T-die at 260 to 280 DEG C, passes through a cooling roll in the range of 20 to 30 DEG C, and the residence time in the cooling roll (casting roll) Is preferably 20 to 40 seconds. If the residence time is short, the cooling of the sheet is insufficient and the crystallization of the cast sheet progresses much and the longitudinal stretching becomes poor. If the residence time is prolonged, not only the production speed is lowered but also, Direction thickness is worse.
In the stretching step, the sheet is stretched by 2.0 to 4.0 times in the machine direction (MD) by passing through a preheating roll at 80 to 100 캜 and contactless irradiation of an IR heater at 500 to 900 캜 and cooled to 20 to 35 캜, Deg.] C, and then biaxially stretched 3.0 to 4.0 times in the transverse direction (TD) at a stretching temperature of 125 to 140 DEG C after preheating.
The stretched sheet can be subjected to heat treatment and relaxation in a range of 200 to 240 ° C in a tenter of 5 to 10 stages. Relaxation is usually given in a range of 1 to 10% with respect to the length in the transverse direction, thereby imparting heat shrinkage and shape stability to the film.
In the present invention, the total film thickness is preferably 50 to 250 mu m. If the thickness is less than 50 탆, sufficient reflectance, durability and weather resistance can not be obtained. If the thickness exceeds 250 탆, the film production processability is greatly reduced without a large increase in reflectance, and delamination may occur in the surface layer.
A backsheet of a solar module having one or more layers of a white film according to the present invention is also included in the scope of the present invention.
That is, a solar module back sheet made of a single layer using the white film of the present invention is also included in the scope of the present invention, and a solar module back sheet including one or more white films of the present invention is also included in the scope of the present invention .
In addition, the present invention can further improve water barrier properties by forming a metal deposition layer on one or both sides of the white film, if necessary. The metal deposition layer can be basically made of a thin film deposited with an oxide of metal, , It is preferable to use an oxide of a metal such as silicon or aluminum in terms of effect, generality and the like. The thickness is preferably selected within the range of 50 to 2000 angstroms, more preferably 100 to 1000 angstroms, though it depends on the kind of metal or metal oxide used.
The white polyester film according to the present invention is excellent in dispersibility of particles by surface coating with inorganic particles, and thus has excellent reflectivity, and thus has excellent durability and reflectance when used for solar cells, and has excellent extrusion process and elongation efficiency in the film forming process A white polyester film having good thickness uniformity and excellent coating properties can be provided.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.
The physical properties of the present invention were measured as follows.
1) I hydrolyse
The film sample was aged for 48 hours in an autoclave under high temperature and high humidity conditions of 120 ° C., 100% RH and 2 bar pressure. After leaving the film sample at room temperature for 2 hours, Respectively.
?: The cut edge of the film is smoothly cut.
DELTA: Very fine cracks occur on the cross section of the cut.
X: Large cracks occur on the cross section of the cut or cracked.
2) Reflectance
The relative reflectance when measured by a spectrophotometer (Varian UV Spectrophotometers Cary 5000) of 100% barium sulfate standard white plate, is a value measured at a visible light of 550 nm. At this time, the measurement angle is 3 ° 20 ", the average time for detecting the signal in the detector is 0.1s, the interval of analysis data is 1 nm, and the scan speed is 600 nm / min.
3) Weatherability
The change of physical properties with time was evaluated by using a weathering tester. The measurement method was measured using the ASTM G154 method. The time point at which the film lost its polymer properties was calculated as a time limit. When exposed to ultraviolet light, 260 hours corresponds to one year.
4) Water vapor permeability (water vapor barrier property)
Was measured using a moisture permeability tester manufactured by MOCON. The measurement method was ASTM F1249 Method (38 ° C, 90% RH).
5) Thermal conductivity (watts / m / K) and heat transfer resistance
ASTM E1530 Guarded Heat Flow Meter Method.
6) Operation
Stable film formation was evaluated and evaluated according to the following criteria.
O: Can be stably formed for more than 24 hours.
DELTA: Film formation can be stably performed for 12 hours to less than 24 hours.
X: Breaking occurs within 12 hours, and the film can not be stably formed.
[Example 1]
14 wt% of inorganic particles (rutile type titanium dioxide having an average particle diameter of 0.5 탆) coated with 86 wt% of polyethylene terephthalate (thermal conductivity 0.24 w / m / k, IV = 0.68) and acrylic resin (thermal conductivity 0.18) To prepare pellets. The prepared pellets were melted at 285 캜, and an unoriented sheet was produced on a casting roll (cooling roll) at 20 캜 while extruding through a tinder. At this time, the residence time in the casting roll was 26.9 seconds, the casting speed was 10.5 m / min, and the air chamber temperature was 18 ° C. The film was stretched 3 times in the longitudinal direction and 3.4 times in the width direction to produce a film having a total thickness of 188 mu m.
The physical properties of the prepared white film were measured and are shown in Table 1 below.
[Example 2]
(Average particle diameter of 0.5 占 퐉) coated with 70% by weight of polyethylene terephthalate (thermal conductivity of 0.24 w / m / k, IV = 0.68) and acrylic resin (thermal conductivity of 0.18) were prepared in the same manner as in Example 1, Of rutile type titanium dioxide) was added in an amount of 30% by weight. The physical properties of the prepared white film were measured and are shown in Table 1 below.
[Example 3]
The resin to be coated with the inorganic particles was mixed with a polyester resin having a thermal conductivity of 0.2 w / m / k (a degree of thermal conductivity of 5 mol% of isophthalic acid copolymerized with the glycol unit in a polyester polymerization process of 0.20 By weight) was used.
[Example 4]
An alumina metal deposition layer (thickness = 1000 ANGSTROM) was formed on one surface of the white film.
[Comparative Example 1]
The resin to be coated was an acrylic resin having a thermal conductivity of 0.28 w / m / k.
[Comparative Example 2]
The resin to be coated was a polyester resin having a thermal conductivity of 0.3 w / m / k.
[Comparative Example 3]
The procedure of Example 1 was repeated except that 9 wt% of the inorganic particles was used.
[Comparative Example 4]
70 wt% of polyethylene terephthalate (thermal conductivity: 0.24 w / m / k, IV = 0.68), 30 wt% of uncoated inorganic particles (rutile type titanium dioxide having an average particle diameter of 0.5 탆) Respectively. The prepared pellets were melted at 285 캜, and an unoriented sheet was produced on a casting roll (cooling roll) at 20 캜 while extruding through a tinder. At this time, the residence time in the casting roll was 26.9 seconds, the casting speed was 10.5 m / min, and the air chamber temperature was 18 ° C. The film was broken due to the difference in the rate of crystallization progression due to the use of a large amount of inorganic particles when the film was formed, which made it impossible to measure the physical properties of the film.
[Table 1]
* In case of Comparative Example 4, it was impossible to operate due to continuous fracture.
As shown in the above table, the white film according to the present invention has a high reflectance and is excellent in hydrolysis resistance, weather resistance, moisture barrier property and workability.
Claims (8)
Wherein the polymer resin coated on the inorganic particles is selected from an acrylic resin or a polyester resin.
[Formula 1]
Kp < Km - R int
(In the formula 1, Kp is of a polymeric resin coating on the inorganic particles, the thermal conductivity, Km is the thermal conductivity of the matrix resin R int is a thermal resistance of the interface between the polymer resin coating on the matrix resin and inorganic particles.)
Wherein the inorganic particles are any one or a mixture of two or more selected from titanium dioxide, barium sulfate, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, magnesium oxide, calcium phosphate, silica, alumina, talc and kaolin.
Wherein the inorganic particles are contained in an amount of 10 to 30% by weight of the entire film.
Wherein the polyester resin is polyethylene terephthalate.
Wherein the polymeric resin coated on the inorganic particles is selected from an acrylic resin or a polyester resin having a glass transition temperature of 20 to 120 DEG C and a coating amount of 0.01 to 0.1 wt% of the inorganic particles.
Wherein the white film has a total film thickness of 50 to 250 占 퐉.
Wherein the solar cell module back sheet further comprises a metal deposition layer on one side or both sides of the white film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110037131A KR101776130B1 (en) | 2011-04-21 | 2011-04-21 | White film for Solar Cell Module |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110037131A KR101776130B1 (en) | 2011-04-21 | 2011-04-21 | White film for Solar Cell Module |
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| Publication Number | Publication Date |
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| KR20120119296A KR20120119296A (en) | 2012-10-31 |
| KR101776130B1 true KR101776130B1 (en) | 2017-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020110037131A KR101776130B1 (en) | 2011-04-21 | 2011-04-21 | White film for Solar Cell Module |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9834713B2 (en) | 2016-02-23 | 2017-12-05 | 3M Innovative Properties Company | Oriented thermally conductive dielectric film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062921A (en) | 2001-06-11 | 2003-03-05 | Bridgestone Corp | Transparent composite film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062921A (en) | 2001-06-11 | 2003-03-05 | Bridgestone Corp | Transparent composite film |
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