KR101413892B1 - Photovoltaic cell module - Google Patents

Abstract

The present invention relates to a photovoltaic module. According to the present invention, it is possible to provide a photovoltaic module having excellent durability which can prevent delamination and discoloration or discoloration of the sealing material constituting a module caused by long-term use or moisture penetration. Further, in the present invention, a photovoltaic module having excellent power generation efficiency can be provided.

Description

{PHOTOVOLTAIC CELL MODULE}

The present invention relates to a photovoltaic module.

Photovoltaic cells are semiconductor devices that can convert light into electricity. When photovoltaic cells are exposed to light, they generate a voltage which causes a subsequent flow of electrons. The magnitude of the electron flow derived from this is proportional to the light impact intensity on the photovoltaic junction formed on the cell surface.

Typical types of photovoltaic cells include silicon wafer photovoltaic cells and thin film photovoltaic cells. A silicon wafer-based photovoltaic cell uses a wafer, which is a semiconductor material produced by using a single crystal or a polycrystalline ingot, as an active layer. In addition, the thin film-based photovoltaic cell uses a continuous layer of a semiconductor material deposited on a substrate, a ferroelectric or the like by a technique such as sputtering or chemical vapor deposition (CVD) as an active layer.

Since both the wafer-based photovoltaic cell and the thin film type photovoltaic cell have brittleness, a load bearing support member is required. The support member may be a top layer such as a ferroelectric that is light transmissive and disposed on top of the photovoltaic cell. The support member may also be a back layer disposed on the back surface of the photovoltaic cell. The photovoltaic module may include an upper layer and a back layer at the same time, which is typically a rigid material such as a glass plate; A flexible material such as a metal film or a metal sheet; Or a plastic material such as polyimide.

The backing layer is typically in the form of a rigid backskin for protecting the back surface of a photovoltaic module, and various materials that can be applied thereto are known. Examples of such materials include ferroelectrics such as glass; Organic fluorine-based polymers such as ethylene tetrafluoroethylene (ETFE), or polyethylene terephthalate (PET) -based materials. The material may be applied to the module alone or in a state covered with a silicon-based and / or oxygen-based material such as SiO _x .

The photovoltaic module may comprise a photovoltaic array that is a collection of photovoltaic cells that are electrically interconnected on a single photovoltaic cell or ferroelectric and / or substrate. The photovoltaic cell or photovoltaic array is attached to the ferroelectric and / or substrate by an encapsulant and encapsulated. The encapsulant is used to protect the cell from the outside and to laminate it on a ferroelectric or a substrate to form an integral module.

Normally, the encapsulant is formed using the same or different encapsulant. Commonly used encapsulants are EVA (ethylene vinyl acetate) based materials or epoxy based materials. Such encapsulants are typically supplied in film form and laminated to the cell and the ferroelectric and / or substrate.

However, conventional encapsulants such as EVA-based materials have poor adhesion to glass and other components of the module. Accordingly, if the photovoltaic module is used for a long period of time, peeling is easily caused between the respective layers of the module, which causes efficiency reduction of the module and corrosion due to moisture penetration. In addition, the conventional encapsulant has a low resistance to ultraviolet rays, causing a problem of discoloration or discoloration when used for a long period of time, lowering the efficiency of the module, generating stress during curing, and damaging the module.

An object of the present invention is to provide a photovoltaic module.

The present invention provides a semiconductor device comprising: an upper substrate; A lower substrate; And a photovoltaic cell or a photovoltaic array sealed by an encapsulating material between the upper substrate and the lower substrate,

Wherein the encapsulating material has a first layer comprising an aryl group-containing silicone resin and a second layer having a water permeability of 1 to 100 g / cm < ² >

Hereinafter, the photovoltaic module of the present invention will be described in detail.

The type of the upper substrate that can be used in the present invention is not particularly limited, and general materials known in this field can be used without limitation. Typically, the upper substrate of the photovoltaic module includes a glass substrate; Fluoropolymer sheet; A cyclic polyolefin-based polymer sheet; A polycarbonate-based polymer sheet; An acrylic polymer sheet; A material having excellent optical transparency, electrical insulation, mechanical strength, physical strength, or chemical strength such as a polyamide-based polymer sheet or a polyester-based polymer sheet is used, but the scope of the present invention is not limited thereto. In the present invention, the thickness and the like of the upper substrate are not particularly limited and may be selected within a general category.

The type of the lower substrate that can be used in the present invention is not particularly limited, and materials commonly used in this field can be used. Typically, the lower substrate may be a metal plate or metal foil such as aluminum; Fluoropolymer sheet; A cyclic polyolefin-based polymer sheet; A polycarbonate-based polymer sheet; An acrylic polymer sheet; A polyamide-based polymer sheet; A weather-resistant sheet such as a polyester-based polymer sheet; Two or more laminated sheets out of the above, or a composite sheet obtained by laminating the above-described sheet and barrier film, and the like are used, but the scope of the present invention is not limited thereto. In the present invention, the thickness and the like of the lower substrate are not particularly limited, and can be adjusted in a general category.

In the photovoltaic module of the present invention, the type of photovoltaic cell or its array sealed with an encapsulating material between the upper and lower substrates is also not particularly limited. In the present invention, the photovoltaic cell or the photovoltaic array may be formed of crystalline silicon such as single crystal or polycrystalline silicon; Amorphous silicon having a structure such as a single bond type or a tandem structure; GaAs, InP, may include a compound semiconductor such as CdTe or CuInSe _2, in some cases, it may also include a poly-crystalline silicon-based, a mixture of thin film amorphous silicon-based or thin-film crystalline silicon and amorphous silicon-based (hybrid) material of the film. However, But is not limited thereto.

The photovoltaic module of the present invention includes an encapsulant that encapsulates a photovoltaic cell or a photovoltaic array. In the present invention, the sealing material is composed of a multilayer structure including a first layer containing an aryl group-containing silicone resin and a second layer of a specific moisture permeability. In the present invention, the sealing material may have a two-layer structure composed of only the first layer and the second layer, and in some cases, it may have a multi-layer structure in addition to the first layer and the second layer . When the encapsulant of the present invention includes a layer other than the first layer and the second layer, the other layer may include an aryl group-containing silicone resin of the present invention described later, and if necessary, an epoxy resin, an EVA resin Or a resin for a conventional encapsulant such as a silicone resin.

The positions of the first layer and the second layer included in the sealing material in the present invention are not particularly limited. In the present invention, for example, the first layer may form the upper layer of the encapsulant and the second layer may form the lower layer of the encapsulant. The structure of the encapsulating material is controlled as described above so as to exhibit excellent adhesion with the module component and to prevent discoloration or discoloration even when used for a long period of time and to effectively block external moisture or moisture, It is possible to secure durability.

Figs. 1 and 2 are views showing exemplary photovoltaic modules according to the present invention. 1, the photovoltaic module 1 of the present invention includes an upper substrate 10; A lower substrate 11; A photovoltaic cell or photovoltaic array 14 between the upper substrate 10 and the lower substrate 11; And sealing materials 12 and 13 sealing the photovoltaic cell or the photovoltaic array 14. When the module 1 of the present invention has the structure of FIG. 1, the photovoltaic cell or the photovoltaic array 14 may include a silicon-based material. 1, the first layer included in the encapsulant may be any one of two layers 12a, 12b encapsulating photovoltaic or photovoltaic arrays 14, and in some cases, Both of the two layers 12a and 12b may form a first layer. In addition, the second layer blocking the penetration of moisture or moisture outside may form the lower layer 13.

2 is a view showing a photovoltaic module 2 according to another example of the present invention. 2, the module 2 of the present invention comprises an upper substrate 10; A lower substrate 11; A photovoltaic or photovoltaic array 24; And sealing materials (12, 13) sealing the photovoltaic cell or array (24). In the structure of FIG. 2, the photovoltaic cell or its array 24 may be a layer of a compound semiconductor. 2, the encapsulant may include a first layer 12 encapsulating the photovoltaic cell or photovoltaic array 24 and a second layer forming a bottom layer 13.

The kind of the aryl group-containing silicone resin contained in the first layer of the encapsulating material of the present invention is not particularly limited as long as it is excellent in adhesion to components of the module and excellent in light resistance, moisture resistance, durability and weather resistance.

In the present invention, it is particularly preferable to use an aryl group-containing silicone resin satisfying the condition of the following general formula (1) in the first layer.

[Formula 1]

X? 0.15

In the general formula (1), X represents the molar ratio (aryl group / Si) of the total aryl groups contained in the resin to the total silicon atoms contained in the resin.

In the present invention, X may preferably be 0.2 or more, more preferably 0.3 or more.

In the present invention, the aryl group contained in the silicone resin may preferably be a phenyl group. By controlling the molar ratio of the aryl groups in the present invention as described above, it is possible to provide an encapsulant having excellent light extraction efficiency, adhesive moisture permeability to a module component, and durability. In the present invention, the upper limit of the molar ratio of the aryl group is not particularly limited, but if it is 15 or more, the viscosity of the resin is high, resulting in poor processability and low impact resistance after curing

In one example of the present invention, the aryl group-containing silicone resin may be a resin represented by an average composition formula represented by the following formula (1) and containing a siloxane unit represented by the following formula (2) or (3)

[Chemical Formula 1]

^{(R 1 R 2 R 3 SiO} 1/2) a (R 4 R 5 SiO 2/2) b (R 6 SiO 3/2) c (SiO 4/2) d

(2)

^{_{(R 7 R 8 SiO 2/}} 2)

(3)

(R ⁹ SiO _3/2)

In the above Chemical Formulas 1 to 3, R ¹ to R ⁶ are substituents directly bonded to the silicon atom, and each independently represents alkyl, aryl, hydrogen, hydroxy, epoxy, acrylic, isocyanate, alkoxy, R at least one of the ¹ to R ⁶ represents an aryl, a is from 0 to 0.6, b is from 0 to 0.98, c is from 0 to 0.8, d is from 0 to 0.4, a + b + c + d is 1 , R ⁷ and R ⁸ are each independently alkyl or aryl, R ⁹ is aryl, b and c are not simultaneously 0, and R ⁷ and R ⁸ Lt; / RTI > represents aryl.

In the present specification, the expression of the silicone resin as the average composition formula of the formula (1) means that the sealing material includes a single silicone resin having the average composition formula of the formula (1) as well as the sealing material contains a plurality of silicone resin components, When the average of the composition of the components is taken, the case represented by the formula (1) is also included.

A silicone resin represented by the average composition formula of the formula (1) in the invention is represented by ^{(R 1 R 2 R 3 SiO} 1/2) a monofunctional siloxane unit (M ^{unit), (R 4 R 5 SiO} 2/2) represented by the a bifunctional siloxane unit (D unit) _{^{is, (R 6 SiO 3/2}} ) 4 -functional siloxane unit (Q unit) represented by the trifunctional siloxane unit (T unit), and (SiO _4/2) represented by the , And at least one siloxane unit of the D unit or the T unit may be represented by the formula (2) or (3).

In the average composition formula of formula (1), R ¹ to R ⁶ are substituents directly bonded to silicon atoms, preferably alkyl or aryl, and may be hydrogen, hydroxy, epoxy, acrylic, isocyanate, ≪ / RTI >

In the above formula (1), alkyl means straight chain, branched or cyclic alkyl having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, , Butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl or decyl, and preferably methyl.

In the above formula (1), alkoxy means straight chain, branched or cyclic alkoxy having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, specifically methoxy, ethoxy, Propoxy, isopropoxy, butoxy, isobutoxy or tert-butoxy, and is preferably methoxy or ethoxy.

In the above formula (1), alkenyl means alkenyl having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms, specifically, a vinyl group, an allyl group, a propenyl group, , A butenyl group, a hexenyl group, a cyclohexenyl group or an octenyl group, and preferably a vinyl group or an allyl group.

In the above formula (1), aryl is an aryl having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, specifically, phenyl, tolyl, xylyl or naphthyl, .

A, b, c and d represent the mole fraction of each siloxane unit. In the average composition formula of formula (1), a, b, c and d have a total of 1, and b and c are not simultaneously 0. Specifically, a is 0 to 0.6, preferably 0 to 0.5, b is 0 to 0.98, preferably 0 to 0.9, and c is 0 to 0.8, preferably 0 to 0.7, in the average composition formula of the formula And d is 0 to 0.4, preferably 0 to 0.2. In the present invention, the distribution ratios of the M, D, T and Q units in the silicone resin are controlled as described above to provide a sealant excellent in adhesion to module parts, moisture resistance, moisture permeability, weather resistance, light resistance, hardness and ultraviolet ray resistance It is possible to provide ashes.

In the present invention, the silicone resin may contain at least one aryl in the molecular structure in consideration of physical properties such as light extraction efficiency, water vapor-permeability and hardness, as shown by the average composition formula of formula (1) Lt; / RTI >

In the silicone resin of the present invention, the aryl is preferably contained in the D unit or the T unit, more preferably the aryl contained in the silicone resin of the average composition formula of the formula (1) is included in the D and / or T unit, The D and T units may have a specific structure, that is, a structure represented by the above formulas (2) and (3).

In the above general formulas (2) and (3), alkyl is preferably alkyl having 1 to 8 carbon atoms, more preferably alkyl having 1 to 4 carbon atoms, more preferably methyl.

In the above formulas (2) and (3), aryl is preferably aryl having 6 to 12 carbon atoms, more preferably phenyl.

In the present invention, the unit represented by the general formula (2) may be a bifunctional siloxane unit (D unit) contained in the silicone resin, and preferably a siloxane unit represented by the following general formula (4) or (5)

[Chemical Formula 4]

(MePhSiO _2/2)

[Chemical Formula 5]

(Ph ₂ SiO _2/2)

In Formula 4 or 5, Me represents methyl and Ph represents phenyl.

In the present invention, the unit of the formula (3) may be a trifunctional siloxane unit (T unit) contained in the silicone resin, preferably a unit represented by the following formula (6).

[Chemical Formula 6]

(PhSiO _3/2)

In the above formula (6), Ph represents phenyl.

A silicone resin represented by the average composition formula of formula (I) in the present invention, weight-average molecular weight may be a (M _w Weight Average Molecular Weight) of 500 to 200,000, preferably from 1,000 to 200,000. In the present invention, the weight average molecular weight of the resin can be adjusted as described above to provide an encapsulant having excellent workability or workability in the encapsulation process and excellent in hardness, light resistance, and durability. The term " weight average molecular weight " in the present invention means a value converted to standard polystyrene measured by gel permeation chromatography (GPC).

In the present invention, the silicone resin contained in the first layer is not particularly limited as long as each of the above-mentioned conditions is satisfied. The silicone resin of the present invention may have an average composition formula specifically, but is not limited thereto.

_{(ViMe 2 SiO 1/2)} 2 (Me 2 SiO 2/2) 30 (MePhSiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 3 (MePhSiO 2/2) 30 (Me 2 SiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 5 (Ph 2 SiO 2/2) 20 (Me 2 SiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (EpSiO 3/2) 5 (Ph 2 SiO 2/2) 10 (Me 2 SiO 2/2) 10

_{(ViMe 2 SiO 1/2)} 3 (PhSiO 3/2) 5

_{(ViMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10 (MeSiO 3/2) 2 (Me 2 SiO 2/2) 5

_{(ViMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10 (MeEpSiO 2/2) 5

_{(HMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10

_{(HMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10 (MeEpSiO 2/2) 5

_{(HMe 2 SiO 1/2)} 2 (Ph 2 SiO2 / 2) 1.5

_{(HMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 5 (Me 2 SiO 2/2) 5

_{(PhSiO 3/2) 10 (} MePhSiO 2/2) 10 (Me 2 SiO 2/2) 10

_{(PhSiO 3/2) 5 (} EpMeSiO 2/2) 2 (Me 2 SiO 2/2) 10

_{(PhSiO 3/2) 5 (} AcSiO 3/2) 5 (Me 2 SiO 2/2) 10

_{(AcSiO 3/2) 5 (} Me 2 SiO 2/2) 10 (Ph 2 SiO 2/2) 5

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 2 (Ph 2 SiO 2/2) 10 (Me 2 SiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (EpSiO 3/2) 3 (MePhSiO 2/2) 10 (Me 2 SiO 2/2) 20

_{(ViMe 2 SiO 1/2)} 3 (Me 2 SiO 2/2) 2 (PhSiO 3/2) 4 (MeSiO 3/2) 6

_{(HMe 2 SiO 1/2)} 2 (PhMeSiO 2/2) 1.5

Here, Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, Ac represents an acryl group, and Ep represents an epoxy group.

In the present invention, the method of forming the encapsulant to include the silicone resin as described above is not particularly limited. In the present invention, for example, an addition curable silicone composition; Condensation or polycondensation silicone composition; It is possible to appropriately employ various materials known in the field such as an ultraviolet ray curable silicone composition or a peroxide vulcanized silicone composition to form an encapsulant containing the silicone resin as described above, and an addition curable silicone composition; Condensation or polycondensation silicone composition; Or an ultraviolet ray curable silicone composition is preferably used, but is not limited thereto.

The addition-curable silicone composition is a composition capable of forming a silicone resin through a hydrosilylation reaction. When the composition is used, an addition-curable silicone composition containing an organosilicon compound having a hydrogen atom (Si-H group) And an organosilicon compound having an alkenyl group bonded to a silicon atom are reacted in the presence of a catalyst to prepare a silicone resin.

In the case of the condensation or polycondensation-curable silicone composition, the organosilane having a hydrolyzable functional group such as -Cl-OCH ₃ , -OC (O) CH ₃ , -N (CH ₃ ) ₂ , -NHCOCH ₃ or -SCH ₃ , Or a siloxane may be subjected to a hydrolysis or condensation reaction to produce a silicone resin.

Further, in the case of the ultraviolet ray curable silicone composition, a functional group capable of initiating polymerization reaction by ultraviolet rays, for example, a silicon compound such as silane or siloxane containing (meth) acrylic or vinyl or a hydrolyzate thereof is hydrolyzed or condensed A silicone resin can be prepared by applying to the reaction, and irradiated with ultraviolet rays.

In this field, various addition curing type which can be selected according to the composition of the desired silicone resin; Condensation or polycondensation curing type; Or an ultraviolet curable silicone composition; And conditions and reaction additives for preparing a silicone resin using such a composition are known. In the present invention, the first layer containing the silicone resin of the above-mentioned formula (1) can be formed by appropriately adopting the above-described method.

The encapsulant of the present invention also includes a second layer having a certain range of moisture permeability. In the present invention, the moisture permeability of the second layer may preferably be 1 to 100 g / cm ² · day, more preferably 1 to 50 g / cm ² · day. As described above, the second layer in the invention can form a lower layer of the encapsulant, effectively preventing external moisture or moisture from penetrating into the module. In the present invention, the moisture permeability can be measured with a mock-up equipment.

In the present invention, the material constituting the second layer is not particularly limited as long as it can exhibit the moisture permeability in the above-mentioned range.

In the present invention, the second layer may be a polymer resin such as EVA or polyolefin resin.

In the present invention, the second layer is formed of an aryl group-containing silicone resin, preferably a phenyl group-containing silicone resin as in the case of the first layer, by controlling the content of the aryl group contained in the resin, It is preferable to form a second layer having a moisture permeability.

In one example of the present invention, the aryl group-containing silicone resin constituting the second layer may satisfy the condition of the following general formula (3).

[Formula 3]

Y? 0.4

In the general formula 3, Y represents the average molar ratio (aryl group / Si) of the total aryl groups contained in the resin to the total silicon atoms contained in the silicone resin.

In the present invention, Y may preferably be 0.45 or more, more preferably 0.5 or more. In the present invention, the proportion of the aryl in the silicone resin contained in the second layer is controlled as described above, so that the second layer can exhibit excellent moisture and moisture barrier effect. In the present invention, the upper limit of the average molar ratio of the aryl group of the silicone resin constituting the second layer is not particularly limited. That is, in the present invention, the higher the average molar ratio of the aryl group of the resin of the second layer, the more excellent water or moisture barrier effect can be exhibited, and the upper limit can be appropriately adjusted in consideration of workability and the like.

More specifically, the silicone resin forming the second layer in the present invention may be a silicone resin represented by an average composition formula of the following formula (7).

(7)

^{(R 10 R 11 R 12 SiO} 1/2) e (R 13 R 14 SiO 2/2) f (R 15 SiO 3/2) g (SiO 4/2) h

Wherein R ¹⁰ to R ¹⁵ are substituents directly bonded to the silicon atom and each independently represents alkyl, aryl, hydrogen, hydroxy, epoxy, acrylic, isocyanate, alkoxy or alkenyl, R ¹⁰ and to R ¹⁵ one or more of aryl, e = 0 to 0.6, and f is 0 to 0.98, g = 0 to 0.8, h is from 0 to 0.4, a stage e + f + g + h is one.

In the present specification, the silicone resin forming the second layer is represented by the average composition formula of the above formula (7), not only the case where the single silicone resin contained in the second layer is represented by the formula (7) When the resin component is present, taking the average of the composition of the resin component, the case represented by the formula (7) is also included.

In the present invention, the more specific types of R ¹⁰ to R ¹⁵ and the preferable examples thereof in the average composition formula of the formula (7) are the same as those of R ¹ to R ⁶ .

In the formula (7), e, f, g and h are mole fractions of M, D, T and Q units constituting the silicone resin, e is 0 to 0.6, preferably 0 to 0.5, 0.98, preferably 0.2 to 0.9, g is 0 to 0.8, preferably 0.2 to 0.7, and h is 0 to 0.4, preferably 0 to 0.2. In the present invention, the distribution ratios of the M, D, T, and Q units in the silicone resin of the second layer are controlled as described above, and the adhesive properties, moisture resistance, moisture permeability, weather resistance, light resistance, hardness, Can provide an excellent sealing material.

In the silicone resin of the second layer of the present invention, the aryl may be included in the D unit or the T unit similarly to the silicone resin of the first layer, and preferably the aryl contained in the silicone resin of the average composition formula of the formula May be included in the D unit represented by the following formula (8) and / or the T unit represented by the following formula (9).

[Chemical Formula 8]

R ¹⁶ R ¹⁷ SiO _2/2

[Chemical Formula 9]

R ¹⁸ SiO _3/2

In the general formulas (8) and (9), R ¹⁶ and R ¹⁷ are each independently alkyl or aryl, and at least one of R ¹⁶ and R ¹⁷ is aryl and R ¹⁸ is aryl.

In the above formulas (8) and (9), more specific examples and preferable examples of the alkyl and aryl are the same as those in the above formulas (2) and (3).

In the present invention, the siloxane unit of formula (8) may more preferably be a bifunctional siloxane unit of formula (10) or (11), and the siloxane unit of formula (9) may be a siloxane unit of formula (12)

[Chemical formula 10]

(MePhSiO _2/2)

(11)

(Ph ₂ SiO _2/2)

[Chemical Formula 12]

(PhSiO _3/2)

In the above formulas 10 to 12, Me represents methyl and Ph represents phenyl.

A silicone resin represented by the average composition formula of the formula (4) in the present invention, weight-average molecular weight may be a (M _w Weight Average Molecular Weight) of 500 to 200,000, preferably from 1,000 to 200,000. In the present invention, the weight average molecular weight of the resin can be adjusted as described above to provide an encapsulant having excellent workability or workability in the encapsulation process and excellent in hardness, light resistance, and durability.

In the present invention, the silicone resin contained in the second layer is not particularly limited as long as each of the above-mentioned conditions is satisfied. The silicone resin of the present invention may have an average composition formula specifically, but is not limited thereto.

_{(ViMe 2 SiO 1/2)} 2 (Me 2 SiO 2/2) 30 (MePhSiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 3 (MePhSiO 2/2) 30 (Me 2 SiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 5 (Ph 2 SiO 2/2) 20 (Me 2 SiO 2/2) 30

_{(ViMe 2 SiO 1/2)} 2 (EpSiO 3/2) 5 (Ph 2 SiO 2/2) 10 (Me 2 SiO 2/2) 10

_{(ViMe 2 SiO 1/2)} 3 (PhSiO 3/2) 5

_{(ViMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10 (MeSiO 3/2) 2 (Me 2 SiO 2/2) 5

_{(ViMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10 (MeEpSiO 2/2) 5

_{(HMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10

_{(HMe 2 SiO 1/2)} 3 (PhSiO 3/2) 10 (MeEpSiO 2/2) 5

_{(HMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 1.5

_{(HMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 5 (Me 2 SiO 2/2) 5

_{(PhSiO 3/2) 10 (} MePhSiO 2/2) 10 (Me 2 SiO 2/2) 10

_{(PhSiO 3/2) 5 (} EpMeSiO 2/2) 2 (Me 2 SiO 2/2) 10

_{(PhSiO 3/2) 5 (} AcSiO 3/2) 5 (Me 2 SiO 2/2) 10

_{(AcSiO 3/2) 5 (} Me 2 SiO 2/2) 10 (Ph 2 SiO 2/2) 5

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 2 (Ph 2 SiO 2/2) 12 (Me 2 SiO 2/2) 10

_{(ViMe 2 SiO 1/2)} 2 (EpMeSiO 2/2) 3 (PhSiO 2/2) 5 (PhMeSiO 2/2) 1

_{(ViMe 2 SiO 1/2)} 2 (PhSiO 2/2) 7 (PhMeSiO 2/2) 1

_{(HMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 1.5

Here, Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, Ac represents an acryl group, and Ep represents an epoxy group.

In the present invention, the method of forming the encapsulant to include the silicone resin as described above is not particularly limited. In the present invention, for example, an addition curable silicone composition selected in accordance with a desired resin composition similarly to the case of the first layer; Condensation or polycondensation silicone composition; The second layer can be formed using an ultraviolet curable silicone composition or a peroxide vulcanized silicone composition or the like.

In the present invention, the method of manufacturing the photovoltaic module including each component is not particularly limited, and various methods known to those skilled in the art can be employed without limitation.

In the present invention, for example, a photocell module can be manufactured by preparing an encapsulating material in the form of a hot-melt sheet or liquid and applying it to an appropriate encapsulating system in consideration of the desired layer structure, It is appropriate to manufacture the module by the direct coating method in terms of the manufacturing cost and the process efficiency.

As used herein, the term " hot melt sheet " refers to a sheet-like formed body made of an encapsulating material. The high-temperature-meltable sheet is a material which is present in an uncured or partially cured state prior to application and which is converted into a fluidity material having a low viscosity by heating with increased strength and flow resistance at room temperature, Lt; / RTI > In this field, a method for producing the above hot-melt sheet using each of the above-mentioned materials is known.

In the present invention, when a high-temperature-melting sheet is used, the module can be manufactured by laminating an upper substrate, a lower substrate, a photovoltaic cell, or a photovoltaic array with a hot-melt sheet according to a desired module structure, and heating and pressing.

Further, in the case of using the liquid material in the present invention, the liquid material may be directly coated at a desired position in the process and then cured to manufacture the photovoltaic module.

However, the method of constructing the module using the encapsulant material as described above in the present invention is not limited to the above-described method.

According to the present invention, it is possible to provide a photovoltaic module having excellent durability which can prevent delamination and discoloration or discoloration of the sealing material constituting a module caused by long-term use or moisture penetration. Further, in the present invention, a photovoltaic module having excellent power generation efficiency can be provided.

1 and 2 are sectional views exemplarily showing a photovoltaic module of the present invention.

Hereinafter, the present invention will be described in more detail by way of examples according to the present invention, but the scope of the present invention is not limited by the following embodiments

Example  One

10 g of the polysiloxane compound B, 200 g of the polysiloxane resin compound C and 60 g of the polysiloxane resin compound D were mixed with 100 g of the polysiloxane compound A and then the catalyst (Platinum (0) -1, 3-divinyl-1,1,3,3-tetramethyldisiloxane) was further added thereto, and the mixture was homogeneously mixed with a stirrer to prepare a sealant first layer resin composition.

[Compound A]

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 2 (Ph 2 SiO 2/2) 10 (Me 2 SiO 2/2) 30

[Compound B]

_{(ViMe 2 SiO 1/2)} 2 (EpSiO 3/2) 3 (MePhSiO 2/2) 10 (Me 2 SiO 2/2) 20

[Compound C]

_{(ViMe 2 SiO 1/2)} 3 (Me 2 SiO 2/2) 2 (PhSiO 3/2) 4 (MeSiO 3/2) 6

[Compound D]

_{(HMe 2 SiO 1/2)} 2 (PhMeSiO 2/2) 1.5

After mixing 10 g of the polysiloxane compound F, 200 g of the polysiloxane resin compound G and 60 g of the polysiloxane resin compound H with 100 g of the polysiloxane compound E, the catalyst (Platinum (0) -1, 3-divinyl-1,1,3,3-tetramethyldisiloxane) was further added thereto, and the mixture was homogeneously mixed with a stirrer to prepare a second layer resin composition for sealing.

[Compound E]

_{(ViMe 2 SiO 1/2)} 2 (ViMeSiO 2/2) 2 (Ph 2 SiO 2/2) 12 (Me 2 SiO 2/2) 10

[Compound F]

_{(ViMe 2 SiO 1/2)} 2 (EpMeSiO 2/2) 3 (PhSiO 2/2) 5 (PhMeSiO 2/2) 1

[Compound G]

_{(ViMe 2 SiO 1/2)} 2 (PhSiO 2/2) 7 (PhMeSiO 2/2) 1

[Compound H]

_{(HMe 2 SiO 1/2)} 2 (Ph 2 SiO 2/2) 1.5

The encapsulant first layer resin composition was applied to a glass substrate for a photovoltaic module and cured at 100 ° C for 1 hour. Then, the photoelectric conversion element was placed on the cured coating liquid and the encapsulating material second layer resin composition was applied again. Thereafter, the applied coating liquid was cured at 150 DEG C for 1 hour, and then the back sheet was thermally pressed to produce a photovoltaic module.

Example  2

Encapsulant A photovoltaic module was prepared in the same manner as in Example 1 except that 50 g of TiO ₂ was mixed with the second layer resin composition

Example  3

Encapsulant material A photovoltaic module was produced in the same manner as in Example 1 except that EVA resin was used in place of the second-layer resin composition.

Comparative Example  One

Instead of using the sealing resin first layer resin composition and the second layer resin composition prepared in Example 1 and instead using a sheet for an encapsulating material of EVA series which is commonly used as a sealing material for photovoltaic cells, the encapsulating material photoelectric conversion element was encapsulated , A photovoltaic module was manufactured in the same manner as in Example 1

Comparative Example  2

A siloxane composition was prepared by mixing the compounds represented by the following formulas (I) to (K) as the polysiloxane compound synthesized in a known manner (compounding amount: 100 g of compound I, 20 g of compound J, 50 g of compound K). Then, a catalyst (Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was added to the composition in such an amount that the content of Pt (0) was 20 ppm, To prepare a resin composition.

(I)

_{(ViPh 2 SiO 1/2)} 2 (Me 2 SiO 2/2) 20

[Chemical Formula J]

_{(ViPh 2 SiO 1/2)} 3 (MeSiO 3/2) 10

[Chemical formula K]

_{(HMe 2 SiO 1/2)} 2 (HMeSiO 2/2) 2 (Me 2 SiO 2/2) 10

In the above formula, Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group.

A photovoltaic module was fabricated in the same manner as in Example 1 except that the second layer resin composition for encapsulant prepared in Example 1 was not used and instead the above composition was used as the first layer resin composition.

Test Example

1. Power evaluation of photovoltaic modules

The efficiencies of the photovoltaic modules manufactured in Examples and Comparative Examples were examined using a sum simulator. Specifically, a light source of about 1 kW was irradiated to the glass substrate side of the manufactured module for the same time, and the power generation amount of the photovoltaic module was measured. The measured results are summarized in Table 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Power generation efficiency 9.3% 9.5% 9.5% 9.0%

2. Evaluation of moisture permeability

A 1 mm thick specimen of the encapsulating material layer 2 was prepared, and water permeability was measured using a Mock instrument. The results are shown in Table 2 below.

3. Endurance reliability evaluation

The durability reliability under the high temperature and high humidity conditions was measured for each of the above specimens in the following manner. Specifically, the composition of Example 1, Comparative Example 1, and Comparative Example 2 was coated on an acrylic plastic substrate, cured, left at 85 DEG C / 85% for 500 hours, and reliability was measured by a fill test method. 2.

<Evaluation Criteria>

O: Adhesion of 15 gf / mm or more

X: Adhesion less than 15 gf / mm

4. Evaluation of UV resistance (Q-UV evaluation)

Each of the specimens was irradiated with light at 60 ° C for 3 days using Q-UVA (340 nm, 0.89 W / cm ² ) equipment to evaluate the occurrence of yellowing, and the results are shown below.

<Evaluation Criteria>

O: 450 nm after light irradiation Absorption rate less than 5%

X: 450 nm after light irradiation Absorption rate: 5% or more

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Moisture permeability
(g / cm &lt; ² &gt; .day) 20 25 15 10 120 Endurance reliability O O O O X UV resistance O O O X O

1, 2: photovoltaic module 10: upper substrate
11: lower substrate 14, 24: active layer
12, 12a, 12b, 13: sealing material

Claims (13)

An upper substrate; A lower substrate; And a photovoltaic cell or a photovoltaic array sealed by an encapsulating material between the upper substrate and the lower substrate,
Wherein the sealing material has a first layer containing an aryl group-containing silicone resin and a second layer having a water permeability of 1 to 100 g / cm ² · day. The photovoltaic module of claim 1 wherein the first layer forms an upper layer of the encapsulant and the second layer forms a lower layer of the encapsulant. The photovoltaic module according to claim 1, wherein the aryl group-containing silicone resin contained in the first layer satisfies the following general formula (1):
[Formula 1]
X? 0.15
In the general formula (1), X represents the molar ratio (aryl group / Si) of the total aryl groups contained in the resin to the total silicon atoms contained in the resin. 4. The photovoltaic module according to claim 3, wherein the aryl group-containing silicone resin is a resin represented by an average composition formula of the following formula (1), and is a resin comprising a siloxane unit represented by the following formula (2)
[Chemical Formula 1]
^{(R 1 R 2 R 3 SiO} 1/2) a (R 4 R 5 SiO 2/2) b (R 6 SiO 3/2) c (SiO 4/2) d
(2)
_{^{(R 7 R 8 SiO 2/}} 2)
(3)
(R ⁹ SiO _3/2)
In the above Chemical Formulas 1 to 3, R ¹ to R ⁶ are substituents directly bonded to silicon atoms, and each independently represents alkyl, aryl, hydrogen, hydroxy, epoxy, acryl, isocyanate, alkoxy, or alkenyl, R at least one of the ¹ to R ⁶ represents an aryl, a is from 0 to 0.6, b is from 0 to 0.98, c is from 0 to 0.8, d is from 0 to 0.4, a + b + c + d is 1 , R ⁷ and R ⁸ are each independently alkyl or aryl, R ⁹ is aryl, b and c are not simultaneously 0, and R ⁷ and R ⁸ Lt; / RTI &gt; represents aryl. 5. The photovoltaic module according to claim 4, wherein the total aryl group contained in the aryl group-containing silicone resin is contained in the siloxane unit of formula (2) or the siloxane unit of formula (3). The photovoltaic module of claim 5, wherein the siloxane unit of formula (2) is a siloxane unit of formula (4) or (5) and the siloxane unit of formula (3)
[Chemical Formula 4]
(MePhSiO _2/2)
[Chemical Formula 5]
(Ph ₂ SiO _2/2)
[Chemical Formula 6]
(PhSiO _3/2)
In the above Chemical Formulas 4 to 6, Me represents methyl and Ph represents phenyl. The photovoltaic module according to claim 1, wherein the aryl group-containing silicone resin has a weight average molecular weight of 500 to 200,000. The photovoltaic module according to claim 1, wherein the second layer comprises an aryl group-containing silicone resin satisfying the following general formula (3):
[Formula 3]
Y? 0.4
In the general formula 3, Y represents the average molar ratio (aryl group / Si) of the total aryl groups contained in the resin to the total silicon atoms contained in the silicone resin of the second layer. 9. The photovoltaic module according to claim 8, wherein the aryl group-containing silicone resin contained in the second layer is a silicone resin represented by an average composition formula of the following formula (7)
(7)
^{(R 10 R 11 R 12 SiO} 1/2) e (R 13 R 14 SiO 2/2) f (R 15 SiO 3/2) g (SiO 4/2) h
Wherein R ¹⁰ to R ¹⁵ are substituents directly bonded to the silicon atom and each independently represents alkyl, aryl, hydrogen, hydroxy, epoxy, acrylic, isocyanate, alkoxy or alkenyl, R ¹⁰ and to R ¹⁵ one or more of aryl, e = 0 to 0.6, and f is 0 to 0.98, g = 0 to 0.8, h is from 0 to 0.4, a stage e + f + g + h is one. The photovoltaic module according to claim 9, wherein the silicone resin contained in the second layer comprises a siloxane unit represented by the following formula (8) or a siloxane unit represented by the following formula (9):
[Chemical Formula 8]
R ¹⁶ R ¹⁷ SiO _2/2
[Chemical Formula 9]
R ¹⁸ SiO _3/2
In the general formulas (8) and (9), R ¹⁶ and R ¹⁷ are each independently alkyl or aryl, and at least one of R ¹⁶ and R ¹⁷ is aryl and R ¹⁸ is aryl. The photovoltaic module of claim 10, wherein the siloxane unit of formula (8) is a siloxane unit of formula (10) or (11) and the siloxane unit of formula (9)
[Chemical formula 10]
(MePhSiO _2/2)
(11)
(Ph ₂ SiO _2/2)
[Chemical Formula 12]
(PhSiO _3/2)
In the above formulas 10 to 12, Me represents methyl and Ph represents phenyl. The photovoltaic module according to claim 9, wherein the silicone resin represented by the average composition formula (7) has a weight average molecular weight of 500 to 200,000. The photovoltaic module according to claim 1, wherein the second layer comprises an ethylene vinyl acetate (EVA) -based or polyolefin-based polymer resin.

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