KR20120057503A - Encapsulation material composition for photovoltaic cell module and photovoltaic cell module comprising the same - Google Patents

Abstract

PURPOSE: An encapsulant composition is provided to have excellent transparence, thermal stability, UV stability and impact resistance, and to have excellent adhesion with other parts like glass, module, etc. CONSTITUTION: An encapsulant composition comprises ethylene-alpha-olefin copolymer, and silane-modified ethylene-alpha-olefin copolymer. The melt flow index(MI) of the ethylene-alpha-olefin copolymer satisfying formula 1: Re × Rc <= 1.0 is 0.2-50 g/10min. The density of the ethylene-alpha-olefin copolymer is 0.85-0.91 g/cm^3, and the distribution of molecular weight is 1.5-3.5. The amount of the silane- modified ethylene-olefin copolymer is 10-900 parts by weight, on the basis of 100.0 parts by weight of the ethylene-alpha-olefin copolymer.

Description

Encapsulation material composition for photovoltaic cell module and photovoltaic cell module comprising the same

The present invention relates to an encapsulant composition, an encapsulant and a photovoltaic module comprising the same.

Photovoltaic cells or solar cells are semiconductor devices that can convert light into electricity. Typically, photovoltaic cells, when exposed to light, generate a voltage through the included terminals, causing a subsequent flow of electrons. The magnitude of the flow of electrons in the above is proportional to the intensity of light impingement on the photovoltaic junction formed on the cell surface.

Representative types of photovoltaic cells known to date include silicon wafer-based photovoltaic cells and thin film photovoltaic cells. In the above, the wafer is a semiconductor material manufactured using a single crystal or polycrystalline ingot or the like. Moreover, the photovoltaic device of a thin film type | system | group photovoltaic cell is a continuous layer of the semiconductor material deposited on the board | substrate, ferroelectric, etc. by techniques, such as sputtering or chemical vapor deposition (CVD).

Since both wafer type photovoltaic cells and thin film type photovoltaic cells have brittleness, a load bearing member for supporting a battery is required. The support member may be an upper layer (eg, ferroelectric) that is light transmissive and disposed above the photovoltaic cell. Alternatively, the support member may be a back layer disposed on the rear surface of the photovoltaic cell. The photovoltaic module can include such top and back layers at the same time, which typically includes a rigid material such as a glass plate; Flexible materials such as metal films or metal sheets; Or a suitable plastic material such as polyimide.

In the above, the back layer (ex. Substrate) is usually in the form of a rigid back skin for protecting the back side of the photovoltaic module. Various materials are known which can be applied to such substrates, for example ferroelectrics (eg glass), organic fluoropolymers (eg ethylene tetrafluoroethylene (ETFE), Tedlar) or polyethylene terephthalate (PET) -based material is included. Such a material may be applied to the module alone, or may be applied in a state covered with a silicon-based and / or oxygen-based material (ex. SiOx).

The photovoltaic module or solar cell module comprises a single photovoltaic cell or a collection of photovoltaic cells (photovoltaic arrays) electrically interconnected on the ferroelectric and / or substrate. Such photovoltaic cells or photovoltaic arrays are encapsulated by being attached to a ferroelectric and / or a substrate by an encapsulant. The encapsulant is used to protect the battery from the external environment, to encapsulate the battery, and to laminate the ferroelectric or the substrate to form an integrated module.

Typically, the encapsulant can be formed using the same or different encapsulant. Currently, the most common encapsulant is an EVA (ethylene vinyl acetate) -based material used to attach and encapsulate a photovoltaic cell or a photovoltaic array to a ferroelectric. The encapsulant is typically supplied in the form of a film and laminated to cells and ferroelectrics and / or substrates.

The encapsulant of the photovoltaic module known to date has the following problems. Encapsulation materials such as EVA-based materials, which are currently used in general, are inferior in adhesion to other parts of glass and modules. Accordingly, when the photovoltaic module is used for a long time, peeling is easily caused between the layers of the module, which causes a decrease in the efficiency of the module or corrosion due to moisture penetration. In addition, the encapsulation materials known to date have a low resistance to ultraviolet rays (UV), so that a problem of discoloration or discoloration occurs when used for a long time, which also lowers the efficiency of the module. In addition, current encapsulation materials, such as EVA-based materials, have a problem in that stress is generated during curing and damage to the module.

An object of the present invention is to provide an encapsulant composition, an encapsulant and a photovoltaic module.

The present invention as a means for solving the above problems, an ethylene-alpha olefin copolymer satisfying the following general formula (1); And a silane-modified ethylene-alphaolefin copolymer.

[Formula 1]

Re × Rc ≤ 1.0

In Formula 1, Re represents kee / kec, Rc represents kcc / kce, and kee represents a growth rate constant when ethylene is added to a growth chain having a terminal active point of ethylene monomer, and kec represents The growth kinetics when the alpha olefin comonomer is added to the growth chain where the terminal active point is the ethylene monomer, kcc represents the growth kinetics when the alpha olefin comonomer is added to the growth chain where the terminal active point is the alpha olefin comonomer Kce represents a growth rate constant when an ethylene monomer is added to a growth chain whose terminal active point is an alphaolefin comonomer.

The present invention provides another encapsulation material comprising the encapsulant composition according to the present invention as another means for solving the above problems.

The present invention as another means for solving the above problems, provides a method for producing an encapsulant comprising the step of molding the encapsulant composition according to the invention in the form of a film.

The present invention is another means for solving the above problems, a support substrate; A photovoltaic cell or photovoltaic array formed on the support substrate; A light receiving substrate formed on the photo cell or the photo cell array; And an encapsulant layer encapsulating the photovoltaic cell or photovoltaic array between the support substrate and the light receiving substrate, the encapsulant layer comprising the encapsulant composition according to the present invention.

The present invention relates to an encapsulant composition and a photovoltaic module comprising the same. In the present invention, it is possible to provide an encapsulant composition which is not only excellent in transparency, thermal stability, ultraviolet stability and impact resistance, but also excellent in adhesiveness to glass and other components of the module.

1 is a cross-sectional view of a photovoltaic module according to an aspect of the present invention.
2 shows a cross-sectional view of a photovoltaic module according to another aspect of the invention.

The present invention is an ethylene-alpha olefin copolymer satisfying the following general formula (1); And a silane-modified ethylene-alphaolefin copolymer.

[Formula 1]

Re × Rc ≤ 1.0

In Formula 1, Re represents kee / kec, Rc represents kcc / kce, and kee represents a growth rate constant when ethylene is added to a growth chain having a terminal active point of ethylene monomer, and kec represents The growth kinetics when the alpha olefin comonomer is added to the growth chain where the terminal active point is the ethylene monomer, kcc represents the growth kinetics when the alpha olefin comonomer is added to the growth chain where the terminal active point is the alpha olefin comonomer Kce represents a growth rate constant when an ethylene monomer is added to a growth chain whose terminal active point is an alphaolefin comonomer.

Hereinafter, the sealing material composition of this invention is demonstrated concretely.

The sealing material composition of this invention is ethylene-alpha olefin copolymer; And a silane-modified ethylene-alpha olefin copolymer, wherein the ethylene-alpha olefin copolymer satisfies the general formula (1).

In the present invention, Re represents kee / kec, Rc represents kcc / kce, and kee represents a growth kinetics constant when ethylene is added to a growth chain each having an end active point of ethylene monomer, and kec has a terminal active point of The growth kinetics constant when the alpha olefin comonomer is added to the growth chain of ethylene monomer, kcc is the growth kinetics constant when the alpha olefin comonomer is added to the growth chain of the terminal active point alpha olefin comonomer, Kce represents a growth rate constant when the ethylene monomer is added to a growth chain whose terminal active point is an alphaolefin comonomer.

Therefore, in the present invention, by measuring the arrangement of the monomers using C13 NMR, the kee, kec, kcc and kce were obtained, respectively, and Re and Rc were calculated through the obtained Re and Rc to the general formula (1). By substitution, the value of the product of Re and Rc can be calculated | required.

In general, when Re × Rc <1.0, the ethylene-alpha olefin copolymer is more likely to be formed as an alternating copolymer. When Re × Rc> 1.0, the ethylene-alpha olefin copolymer is a block copolymer ( It may be formed into a block copolymer.

In the present invention, the alternating copolymer refers to a form in which two monomer components constituting the copolymer are alternately bonded (ex. -ABABABAB-), and the block copolymer is one monomer component polymerized continuously to form a block. Form, and then other monomer components are subsequently polymerized to form blocks (ex. -AAAABBBB-).

Therefore, the ethylene-alpha olefin copolymer according to the present invention may be in the form of a copolymer in which three or more alpha olefin comonomers are not continuously polymerized, and characteristics of the copolymer in which the alpha olefin comonomer is evenly distributed in the polymer backbone Can have

In the present invention, the ethylene-alpha olefin copolymer satisfying the general formula (1) has a silane-modified ethylene-alpha olefin copolymer using the ethylene-alpha olefin copolymer because the alpha olefin comonomer is evenly distributed in the polymer main chain. When manufacturing, it is possible to improve the reaction efficiency through a uniform reaction, thereby improving the physical properties of the encapsulant.

In the present invention, the ethylene-alpha olefin copolymer satisfying the general formula 1 is a transition metal compound represented by the following Formula 1, more specifically, a transition metal compound represented by the following Formula 2 or a transition metal compound represented by the following Formula 3 It may be prepared using a catalyst composition comprising a.

[Formula 1]

In Chemical Formula 1,

R1 and R2 are each independently hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Silyl groups; Alkylaryl groups having 7 to 20 carbon atoms; Arylalkyl groups having 7 to 20 carbon atoms; Or a metalloid group of a Group 4 metal substituted with hydrocarbyl, wherein R 1 and R 2 or two R 2 are connected to each other by an alkylidine group including an alkyl having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring. Can form,

Each R 3 is independently hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Alkylaryl groups having 7 to 20 carbon atoms; Arylalkyl groups having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy groups having 6 to 20 carbon atoms; Or an amido group, two or more R3 in the R3 may be connected to each other to form an aliphatic ring or an aromatic ring,

CY1 represents a substituted or unsubstituted aliphatic or aromatic ring, and the substituents substituted in CY1 are halogen; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Alkylaryl groups having 7 to 20 carbon atoms; Arylalkyl groups having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy groups having 6 to 20 carbon atoms; Or an amido group, when there are a plurality of substituents, two or more substituents in the substituents may be connected to each other to form an aliphatic or aromatic ring,

M represents a Group 4 transition metal;

Q1 and Q2 are each independently halogen; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Alkylaryl groups having 7 to 20 carbon atoms; Arylalkyl groups having 7 to 20 carbon atoms; Alkyl amido groups having 1 to 20 carbon atoms; Aryl amido groups having 6 to 20 carbon atoms; Or an alkylidene group having 1 to 20 carbon atoms.

The transition metal compound represented by Chemical Formula 1 may be a transition metal compound represented by Chemical Formula 2 or Chemical Formula 3 as a more preferred compound for controlling the electronic and three-dimensional environment around the metal.

[Formula 2]

(3)

In Chemical Formulas 2 and 3,

R4 and R5 are each independently hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Or silyl group,

Each R 6 is independently hydrogen; halogen; An alkyl group having 1 to 20 carbon atoms; Alkenyl groups having 2 to 20 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Alkylaryl groups having 7 to 20 carbon atoms; Arylalkyl groups having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy groups having 6 to 20 carbon atoms; Or an amido group, wherein two or more R 6 in R 6 may be linked to each other to form an aliphatic or aromatic ring,

Q3 and Q4 are each independently halogen; An alkyl group having 1 to 20 carbon atoms; Alkyl amido groups having 1 to 20 carbon atoms; Or an aryl amido group having 6 to 20 carbon atoms,

M represents a Group 4 transition metal.

The transition metal compound represented by Formula 1 may be a transition metal compound having the following structure as a compound which is more preferred for controlling the electronic and three-dimensional environment around the metal.

In the above structural formula,

Each R 7 independently represents a hydrogen or a methyl group,

Q5 and Q6 each independently represent a methyl group; Dimethyl amido group; Or a chloride group.

In the present invention, the catalyst composition comprising the transition metal compound represented by Formula 1 is a group consisting of a promoter compound represented by Formula 4, a promoter compound represented by Formula 5 below, and a promoter compound represented by Formula 6 It may include one or more selected from.

[Formula 4]

-[Al (R8) -O] n-

[Chemical Formula 5]

D (R9) ₃

[Formula 6]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

Where

R8 and R9 are each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen, n represents an integer of 2 or more,

D represents aluminum or boron,

L represents a neutral or cationic Lewis acid, H represents a hydrogen atom, Z represents a Group 13 element, and A each independently represents one or more hydrogen atoms substituted by halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy Or an unsubstituted aryl group having 6 to 20 carbon atoms; Or an alkyl group having 1 to 20 carbon atoms.

Specific examples of the cocatalyst compound represented by Chemical Formula 4 in the present invention include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane, and preferably methyl aluminoxane.

Specific examples of the cocatalyst compound represented by Chemical Formula 5 in the present invention include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s- Butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, Dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron, and the like, and preferably trimethyl aluminum, triethyl aluminum or triisobutyl aluminum. .

Specific examples of the cocatalyst compound represented by Chemical Formula 6 in the present invention include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium. Umtetra (p-tolyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) Boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluoro Phenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl Ammonium Tetraphenyl Aluminum, Tripropyl Ammonium Tetraphenyl Aluminum, Trimethyl Ammonium Tetra (p-tolyl) Aluminum, Tripropyl Ammonium Tetra (p-tolyl) Aluminum, Triethyl Ammonium Tetra (o, p-dimethylphenyl) Aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniline Umtetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium Tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri Phenyl carbonium tetra (p-trifluoromethylphenyl) boron, a triphenyl carbonium tetrapentafluoro phenyl boron, etc. are mentioned.

In the present invention, the compounds represented by the formula (4) and the formula (5) in the promoter compound may be an alkylating agent, the compound represented by the formula (6) may serve as an activator.

In the present invention, the catalyst composition is present in an activated state by a reaction between the transition metal compound represented by the formula (1) and the aforementioned cocatalyst compound, and may be referred to as an activated catalyst composition. However, since it is known in the art that the catalyst composition is present in an activated state, the term activated catalyst composition is not used separately herein.

In the present invention, the ethylene-alpha olefin copolymer is prepared by using one or more promoters of the transition metal compound represented by Formula 1 and the promoter compound represented by Formulas 4 to 6, and then using ethylene It can be prepared by copolymerizing a monomer and an alphaolefin comonomer.

In the present invention, the method for preparing the catalyst composition is not particularly limited, and for example, may be prepared by the following method.

Firstly mixing the transition metal compound represented by Chemical Formula 1 with the cocatalyst compound represented by Chemical Formula 4 or Chemical Formula 5; And it can be prepared a catalyst composition by the production method comprising the step of mixing the mixture and the promoter compound represented by the formula (6).

In addition, a catalyst composition may be prepared by mixing the transition metal compound represented by Chemical Formula 1 and the cocatalyst compound represented by Chemical Formula 4.

Third, a catalyst composition may be prepared by mixing the transition metal compound represented by Chemical Formula 1 and the cocatalyst compound represented by Chemical Formula 6.

In the first production method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the promoter compound represented by Formula 4 or Formula 5 is 1: 2 to 1: 5000, preferably May be 1:10 to 1: 1,000, more preferably 1:20 to 1: 500. In addition, the molar ratio of the transition metal compound represented by Chemical Formula 1 and the cocatalyst compound represented by Chemical Formula 6 is 1: 1 to 1:25, preferably 1: 1 to 1:10, and more preferably 1: 2. To 1: 5.

When the molar ratio of the cocatalyst compound represented by Formula 4 or Formula 5 to the transition metal compound represented by Formula 1 is less than 1: 2 in the first preparation method, the amount of alkylating agent is very small, so that alkylation of the transition metal compound There is a problem of not fully progressing, and when the ratio exceeds 1: 5000, alkylation of the transition metal compound is performed, but activation of the alkylated transition metal compound is caused by a side reaction between the remaining excess alkylating agent and the activator represented by the formula (6). There is a problem that can not be made completely.

In addition, when the molar ratio of the cocatalyst compound represented by the formula (6) to the transition metal compound represented by the formula (1) is less than 1: 1, the amount of the activator is relatively small to activate the transition metal compound represented by the formula (1). Is not completely made, there is a problem in that the activity of the resulting catalyst composition is inferior, and if it exceeds 1:25, the activation of the transition metal compound represented by the formula (1) is completely made, but due to the excess of the remaining activator catalyst composition There is a problem that the unit price of is not economical or the purity of the polymer produced is poor.

In the second production method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the promoter compound represented by Formula 4 is 1:10 to 1: 10000, preferably 1: 100 to 1: 5000, more preferably 1: 500 to 1: 2000.

When the molar ratio of the cocatalyst compound represented by Chemical Formula 4 to the transition metal compound represented by Chemical Formula 1 is less than 1:10 in the second production method, the amount of alkylating agent is relatively small so that alkylation of the transition metal compound proceeds completely. In case of exceeding 1: 10,000, the alkylation of the transition metal compound represented by Formula 1 is completely performed. However, the excess cost of the catalyst composition is not economical or the purity of the produced polymer is increased. There is a problem falling.

In addition, in the third production method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the cocatalyst compound represented by Formula 6 is 1: 1 to 1:25, preferably 1: 1 to 1:10, more preferably 1: 2 to 1: 5.

When the molar ratio of the cocatalyst compound represented by Chemical Formula 6 to the transition metal compound represented by Chemical Formula 1 is less than 1: 1 in the third manufacturing method, the amount of the activator is relatively small, There is a problem in that the activity of the resulting catalyst composition is not fully activated, and if the activity exceeds 1:25, the transition metal compound is fully activated, but due to the excess amount of the remaining activator, the cost of the catalyst composition is economical. There is a problem that is not or the purity of the polymer produced.

In addition, the transition metal compound represented by Formula 1 and the cocatalyst compound represented by Formulas 4 to 6 may be used in a form supported on silica or alumina.

In the polymerization method of the ethylene-alpha olefin copolymer, the catalyst composition described above may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; It may be used after being dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene. The solvent of the catalyst composition used as described above is preferably treated with a small amount of alkyl aluminum to remove a small amount of water, air, or the like acting as a catalyst poison, and can also be carried out using a promoter.

The type of the alpha olefin comonomer copolymerized with the ethylene monomer using the catalyst composition described above in the present invention is not particularly limited, and not only one double bond but also two diene olefin monomers or two double bonds. A personal triene olefin monomer etc. can also be used.

In the present invention, the alpha olefin comonomer may be an alpha olefin having 3 to 20 carbon atoms. Specific examples of the alpha olefin comonomer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 Dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, or 3-chloromethylstyrene, etc. are mentioned, These monomers can also be used in mixture of 2 or more types. Preferably propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetra At least one selected from the group consisting of decene, 1-hexadecene and 1-atocene, more preferably propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene and 1-octene May be one or more selected from, and most preferably 1-octene. Although the kind of polymerization solvent which melt | dissolves a monomer at this time is not specifically limited, It may be preferable to use n-hexane.

In the present invention, the polymerization method of the ethylene-alpha olefin copolymer is not particularly limited, but a solution process using the catalyst composition may be preferable. In addition, when the catalyst composition is used on an inorganic carrier such as silica or alumina, the ethylene-alpha olefin copolymer may be polymerized in a slurry or gas phase process.

In the present invention, the type of reactor used in the process of producing the ethylene-alpha olefin copolymer is not particularly limited, and may be, for example, a continuous stirred reactor (CSTR) or a continuous flow reactor (PFR). In addition, it may be preferable that two or more reactors are arranged in series or in parallel in the polymerization process of the ethylene-alpha olefin copolymer. In addition, it may be desirable to further include a separator for continuously separating the solvent and the unreacted monomer from the reaction mixture in the manufacturing process of the ethylene-alpha olefin copolymer.

In the ethylene-alphaolefin copolymer of the present invention, the molar ratio of the ethylene monomer and the alpha olefin comonomer is 100: 1 to 1: 100, preferably 10: 1 to 1:10, more preferably 2: 1 to 1 May be five. In the present invention, when the molar ratio of the ethylene monomer and the alpha olefin comonomer exceeds 100: 1 (ex. 110: 1, etc.), the resulting copolymer may have a high density, making it difficult to prepare a low density copolymer. When it exceeds: 100 (ex. 1: 110, etc.), the amount of unreacted comonomer is increased, the conversion rate is lowered, and consequently, the recycling process may be increased in the manufacturing process.

In the present invention, the molar ratio of the monomer and the polymerization solvent suitable for the polymerization reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. Specifically, the molar ratio of the monomer and the polymerization solvent may be 10: 1 to 1: 10000, preferably 5: 1 to 1: 100, more preferably 1: 1 to 1:20. In the present invention, when the molar ratio of the monomer and the polymerization solvent exceeds 10: 1 (ex. 15: 1, etc.), the amount of the solvent is too small to increase the viscosity of the fluid, which may cause a problem in the transport of the produced copolymer. In the case of exceeding 1: 10000 (ex. 1: 11000, etc.), the amount of the solvent may be greater than necessary, such as an increase in equipment and an increase in energy cost due to recycling for the purification of the polymerization solvent.

In the present invention, the density of the ethylene-alpha olefin copolymer prepared as described above may be 0.85 g / cm 3 to 0.91 g / cm 3. When the density of the ethylene-alpha olefin copolymer is less than 0.85 g / cm 3, the crystal region decreases to decrease the heat resistance, and there is a possibility that the workability may deteriorate. When the density of the ethylene-alpha olefin copolymer exceeds 0.91 g / cm 3, the crystal region increases too much to increase transparency. It may be reduced.

In the present invention, the melt flow index (MI) of the ethylene-alpha olefin copolymer is 0.2 g / 10min to 50 g / 10min, preferably 1 g at a temperature of 190 ° C. and a load condition of 2.16 kg according to ASTM D1238. / 10min to 30 g / 10min, more preferably 5 g / 10min to 15 g / 10min. If the melt flow index (MI) of the ethylene-alpha olefin copolymer is less than 0.2 g / 10min, it may be difficult to process the encapsulant due to the increase in molecular weight and viscosity, and when the excess exceeds 50 g / 10min, the molecular weight decreases. There is a risk of deterioration of physical properties.

In the present invention, the molecular weight distribution (Mw / Mn) of the ethylene-alpha olefin copolymer may be 1.5 to 3.5, preferably 2.0 to 3.0. If the molecular weight distribution of the ethylene-alpha olefin copolymer is less than 1.5, the load may increase during extrusion, and if it exceeds 3.5, physical properties such as transparency and adhesiveness may be reduced.

In the present invention, the silane-modified ethylene-alpha olefin copolymer is a copolymer comprising a silane monomer copolymerized in the ethylene-alpha olefin copolymer; Alternatively, the ethylene-alpha olefin copolymer may be in the form of a graft polymer grafted with a silane monomer.

In the present invention, a form copolymerized with the silane-modified ethylene-alpha olefin copolymer; Alternatively, the silane monomers included in the grafted form may be unsaturated silanes including ethylenically unsaturated hydrocarbon groups and hydrolysable functional groups. In the present invention, the silane monomer may be, for example, having a functional group such as vinyl, acrylic, amino, chloro and phenoxy. More specifically, ethylenically unsaturated silanes such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl triacetoxy silane or γ-ketacryloxypropyl trimethoxy silane are preferable, but are not limited thereto.

In the present invention, in order to prepare the silane-modified ethylene-alpha olefin copolymer, a vinyl trimethoxy silane having a vinyl functional group having the easiest polymerization reaction as a silane monomer applied to the ethylene-alpha olefin copolymer is used together with a radical initiator. It may be most desirable.

In the present invention, the silane-based monomer included in the polymerized form in the silane-modified ethylene-alpha olefin copolymer is 0.1 part by weight to 5 parts by weight, preferably 0.5 part by weight based on 100 parts by weight of the silane-modified ethylene-alpha olefin copolymer. To 4.5 parts by weight. When the content of the silane-based compound is less than 0.1 parts by weight, there is a fear that the adhesive properties of the encapsulant composition to be produced may be lowered, if it exceeds 5 parts by weight, in view of the reaction efficiency it is necessary to use more radical initiators, It is difficult to control the physical properties of the sealing material composition, and there is a fear that the physical properties are lowered.

In the present invention, the radical initiator is benzoyl peroxide, di-tributyl peroxide, azobisisobutylonitrile, tributyl hydroperoxide, dicumyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, t -Butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauryl peroxide, t-butyl peracetate liquid peroxide (lupersol 101 , Pennwalt (manufactured) or Percadox-14 (manufactured by AKZO), and the like, preferably t-butyl peracetate liquid peroxide (lupersol 101, Pennwalt company) However, it is not limited thereto.

In the present invention, the radical initiator may be included in an amount of 0.001 part by weight to 5 parts by weight, preferably 0.01 part by weight to 3 parts by weight, based on 100 parts by weight of the silane-based monomer contained in a polymerized form in the silane-modified ethylene-alphaolefin copolymer. have. When the content of the radical initiator is less than 0.001 parts by weight, the amount of reactive radicals may decrease to reduce the reaction efficiency. When the amount of the radical initiator exceeds 5 parts by weight, the amount of reactive radicals may increase to cause side reactions, thereby causing physical properties of the encapsulant composition. There is a risk of deterioration.

In the present invention, the silane-modified ethylene-alpha olefin copolymer may be included in an amount of 10 parts by weight to 900 parts by weight, preferably 20 parts by weight to 500 parts by weight, based on 100 parts by weight of the ethylene-alpha olefin copolymer. When the content of the silane-modified ethylene-alpha olefin copolymer is less than 10 parts by weight, the peeling strength may be reduced due to the decrease in adhesiveness, and when the content of the silane-modified ethylene-alphaolefin copolymer is lower than 900 parts by weight, the peeling strength may be reduced due to the degradation of the physical properties of the polymer. There is.

In order to prepare the silane-modified ethylene-alpha olefin copolymer in the present invention, at least one additive selected from the group consisting of an antioxidant, a UV stabilizer, a filler, and a coloring agent may be added in addition to the radical initiator, and the silane monomer and ethylene-alpha may be added. The polymerization reaction between the olefin copolymers may be preferably carried out under a nitrogen atmosphere of 50 ℃ to 230 ℃.

In the present invention, the encapsulant composition may further include another kind of ethylene-alpha olefin copolymer having a different molecular weight or density from the ethylene-alpha olefin copolymer.

In the present invention, the ethylene-alpha olefin copolymer further included is 10 based on 100 parts by weight of the encapsulant composition including the ethylene-alpha olefin copolymer and the silane-modified ethylene-alpha olefin copolymer satisfying the general formula (1). It may be included in an amount of from 1000 to 500 parts by weight, preferably 50 to 500 parts by weight. If the content of the ethylene-alpha olefin copolymer further included is less than 10 parts by weight, the workability and physical properties may be reduced, and if it is more than 1000 parts by weight, the adhesion may be reduced.

The encapsulant composition of the present invention may further include one or more additives selected from the group consisting of UV absorbers, light stabilizers, antioxidants, glass fever, and glass bubbles.

UV absorbers that can be used in the present invention include 2-hydroxy-4-methoxybenzophenone, 2-2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4-carboxy Benzophenone compounds such as benzophenone or 2-hydroxy-4-N-octoxybenzophenone; Benzotriazole compounds such as 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole or 2- (2-hydroxy-5-methylphenyl) benzotriazole; Salicylic acid ester type compounds, such as phenyl salicylate or p-octylphenyl salicylate, etc. are mentioned, It is not limited to these. In the present invention, the content of the ultraviolet absorber may be 0.05 parts by weight to 1.0 parts by weight, preferably 0.1 parts by weight to 0.8 parts by weight with respect to 100 encapsulation of the encapsulant composition.

The light stabilizer that may be used in the present invention may include a hindered amine compound or a piperidine compound, but is not limited thereto. In the present invention, the content of the light stabilizer may be 0.05 to 1.0 parts by weight, preferably 0.1 to 0.8 parts by weight with respect to 100 encapsulation of the encapsulant composition.

Antioxidants that may be used in the present invention include, but are not limited to, phenolic compounds or phosphite compounds. In the present invention, the content of the antioxidant may be 0.1 parts by weight to 0.5 parts by weight, preferably 0.2 parts by weight to 0.4 parts by weight with respect to 100 encapsulation of the encapsulant composition.

The kind of glass fever or glass bubble which can be used in this invention is not specifically limited, The well-known generally used in this field can be used without a restriction | limiting.

The present invention also relates to an encapsulant comprising the encapsulant composition according to the present invention.

Although the form of the sealing material of this invention is not specifically limited, Preferably it may be a sheet or a film form.

When the shape of the encapsulant of the present invention is in the form of a sheet or film, the thickness of the sheet or film is preferably 0.2 mm to 0.8 mm, but is not limited thereto. In the present invention, when the thickness of the encapsulant sheet or the encapsulant film is less than 0.2 mm, there is a fear that the ability to absorb external shocks may be lowered. As a result, workability and light transmittance may be lowered.

The present invention also relates to a method for producing an encapsulant, comprising molding the encapsulant composition according to the present invention into a sheet or film form.

Molding the encapsulant composition of the present invention comprising the ethylene-alpha olefin copolymer and the silane-modified ethylene-alpha olefin copolymer prepared as described above in the form of a sheet or a film is an extrusion T-die. Alternatively, the method may be performed through a calendering method, but is not limited thereto.

For example, ethylene-alpha olefin copolymer; Silane-modified ethylene-alphaolefin copolymers; And additives such as an ultraviolet absorber or a light stabilizer may be continuously fed into the extruder at the same time to produce an encapsulant in the form of a sheet or a film.

The present invention also provides a support substrate; A photovoltaic cell or photovoltaic array formed on the support substrate; A light receiving substrate formed on the photovoltaic cell or photovoltaic array; And an encapsulant layer encapsulating the photovoltaic cell or photovoltaic array between the support substrate and the light receiving substrate, the encapsulant layer comprising the encapsulant composition according to the present invention.

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

In the present invention, the support substrate serves to protect the back surface of the photovoltaic module from the outside, and weather resistance is required. In this invention, the specific kind of the said support substrate is not specifically limited, For example, metal plates or metal foils, such as aluminum, a fluorine resin sheet, a cyclic polyolefin resin sheet, a polycarbonate resin sheet, and a poly (meth) acrylic resin The composite sheet which laminated | stacked a sheet | seat, a polyamide-type resin sheet, a polyester-type resin sheet, or a weather-resistant film, and a barrier film is mentioned.

The thickness of the support substrate used in the present invention is not particularly limited, and may be, for example, 30 μm to 2,000 μm, preferably 50 μm to 1,000 μm, and more preferably 100 μm to 600 μm. In the present invention, by controlling the thickness of the support substrate in the range of 30 μm to 2,000 μm, the photovoltaic module can be configured to be thinner, and excellent physical properties such as weather resistance of the photovoltaic module can be maintained.

In the present invention, a specific kind of photovoltaic cells formed on the support substrate is not particularly limited as long as it can cause photovoltaic power, and photovoltaic elements generally used in this field may be used. In the present invention, for example, amorphous silicon photovoltaic cells, such as crystalline silicon photovoltaic cells such as monocrystalline silicon, polycrystalline silicon, single-bonded or tandem structures, gallium arsenide (GaAs), indium- Group III-V compound semiconductor photovoltaic cells such as phosphorus (InP) and group II-VI compound semiconductor photovoltaic cells such as cadmium-tellurium (CdTe) and copper-indium-selenide (CuInSe ₂ ), and the like can be used. Film polycrystalline silicon photovoltaic cells, thin film microcrystalline silicon photovoltaic cells, and hybrid photovoltaic cells of thin film crystalline silicon and amorphous silicon may also be used.

In the present invention, the photovoltaic cell can form a photovoltaic array (photovoltaic cell assembly) by wiring connecting the photovoltaic cell and the photovoltaic cell. When sunlight shines on the photovoltaic module of the present invention, electrons (-) and holes (+) are generated inside the photovoltaic cell, and current flows through the wiring connecting the photovoltaic cell and the photovoltaic cell.

In the present invention, the light-receiving substrate formed on the photovoltaic cell or photovoltaic array may perform a function of protecting the inside of the photovoltaic module from wind, external shock or fire, and ensuring long-term reliability upon outdoor exposure of the photovoltaic module. . Specific types of the light-receiving substrate of the present invention are not particularly limited as long as the light-receiving substrate is excellent in light transmittance, electrical insulation, mechanical or physical, and chemical strength. For example, a glass plate, a fluorine resin sheet, a cyclic polyolefin resin sheet, and a polycarbonate A resin sheet, a poly (meth) acrylic resin sheet, a polyamide resin sheet, or a polyester resin sheet can be used. In this invention, although it is preferable to use the glass plate excellent in heat resistance, it is not limited to this.

The thickness of the light-receiving substrate used in the present invention is not particularly limited, and may be, for example, 0.5 mm to 10 mm, preferably 1 mm to 8 mm, more preferably 2 mm to 5 mm. In the present invention, by controlling the thickness of the light-receiving substrate in the range of 0.5 mm to 10 mm, it is possible to configure the photovoltaic module to be thinner, while maintaining excellent properties such as long-term reliability of the photovoltaic module.

In addition, in the present invention, an encapsulant layer encapsulating a photovoltaic cell or a photovoltaic cell array within the photovoltaic module, specifically, between the support substrate and the light receiving substrate, may include the encapsulant composition according to the present invention described above.

As the encapsulant layer of the present invention comprises the encapsulant composition according to the present invention as described above, not only excellent transparency, thermal stability, ultraviolet stability and impact resistance, but also excellent retention of adhesion to the supporting substrate and the light receiving substrate The life of the photovoltaic module can be extended.

In the present invention, the encapsulant layer may be in the form of a single layer, the first layer encapsulating the photovoltaic cell or the photovoltaic array in contact with the light receiving substrate, and the second layer encapsulating the photovoltaic cell or the photovoltaic array in contact with the support substrate. It may be a multilayer form including a.

In the present invention, the light transmittance of the encapsulant layer may be 92% or more, preferably 94% or more. In the present invention, by controlling the light transmittance of the encapsulant layer to 92% or more, it is possible to improve transparency of the photovoltaic cell by providing transparency to the photovoltaic module.

In the present invention, the upper limit of the light transmittance of the encapsulant layer is not particularly limited, and may be preferably closer to 100%. This is because the closer the light transmittance is to 100%, the greater the chance that the photovoltaic cell comes into contact with light can improve the light conversion efficiency of the photovoltaic cell.

In the present invention, the cloudiness (haze) of the encapsulant layer may be 14% or less, preferably 12% or less. In the present invention, by controlling the blurring degree of the encapsulant layer to 14% or less, transparency of the photovoltaic module can be provided to improve the light conversion efficiency of the photovoltaic cell.

In the present invention, the lower limit of the degree of cloudiness of the encapsulant layer is not particularly limited, and may be more preferably closer to 0%. This is because the closer the cloudiness is to 0%, the more light energy comes into contact with the photovoltaic cell, thereby improving the light conversion efficiency of the photovoltaic cell.

In the present invention, a method for measuring the light transmittance and the cloudiness of the encapsulant layer is not particularly limited, and may be based on a means generally used in this field. In the present invention, for example, the light transmittance and haze were measured using a reflectance-transmittance meter (HR-100, manufactured by Murakami Co., Ltd.), but is not limited thereto.

Peel strength of the encapsulant layer in the present invention may be 60 N / 15mm or more.

In the present invention, the peel strength of the encapsulant layer refers to the peel strength measured at a peel rate of 50 mm / min and a peel angle of 90 ° under an atmosphere of 25 ° C. after attaching the encapsulant to the substrate.

Specimens composed of the encapsulant and substrate prepared from the encapsulant composition of the present invention have a peel strength of 60 N / 15 mm or greater, preferably 70 N / 15 mm or greater, measured according to specific conditions, specifically, the conditions of ASTM D903, More preferably, it may be 80 N / 15 mm or more.

In the present invention, the upper limit of the peel strength is not particularly limited, and may be controlled within a range of, for example, 300 N / 15 mm or less, preferably 250 N / 15 mm or less, more preferably 200 N / 15 mm or less. .

The method of measuring the peeling strength of the sealing material layer in this invention is not specifically limited, For example, it can measure by the following method. First, the sealing material of 500 micrometers in thickness is manufactured from the sealing material composition of this invention according to the manufacturing method mentioned above, and the said sealing material is cut | judged to the size of 5 cm x 5 cm (width x length). Thereafter, one side of the encapsulant was attached to a plate glass (thickness: 3 mm), which is a light receiving substrate, and the other side of the encapsulant was attached to a support substrate, and then pressed at a temperature of 150 ° C. for 15 minutes in a vacuum laminator for manufacturing a photovoltaic module. After the sample was prepared, the peel strength can be measured under conditions of a temperature of 25 ° C., a peel rate of 50 mm / min, and a peel angle of 90 ° (condition of ASTM D903) at a time point of 20 minutes. The support substrate is a laminated sheet in which a polyvinyl fluoride resin sheet having a thickness of 38 μm, an aluminum foil having a thickness of 30 μm, and a polyvinyl fluoride resin sheet having a thickness of 38 μm are sequentially stacked.

In the present invention, by controlling the peel strength of the encapsulant layer to 60 N / 15mm or more to maintain excellent adhesion to other components of the glass substrate or photovoltaic module, it is possible to prevent the peeling between each layer of the photovoltaic module, Thereby, the fall of the efficiency of a photovoltaic module and the induction of corrosion by moisture ingress can be prevented.

In addition, the drop impact strength of the encapsulant layer in the present invention may be 1400 g or more.

In the present invention, the drop impact strength of the encapsulant layer represents a drop impact strength measured by a drop impact tester after freely dropping a weight having a diameter of 38 mm at a height of 0.66 m on the encapsulant film having a thickness of 100 μm.

The encapsulant film prepared from the encapsulant composition of the present invention has a drop impact strength (X2) of 1400 g or more, preferably 1800 g or more, more preferably measured according to specific conditions, specifically, the conditions of ASTM D1709A. May be at least 2000 g.

In the present invention, the upper limit of the drop impact strength is not particularly limited, and may be controlled within a range of, for example, 4000 g or less, preferably 3000 g or less, more preferably 2500 g or less.

The method for measuring the drop impact strength of the encapsulant layer in the present invention is not particularly limited, and can be measured, for example, in the following manner. First, an encapsulant film having a thickness of 100 μm is prepared from the encapsulant composition of the present invention, and the encapsulant film is cut into a size of 5 cm × 5 cm (width × length) to prepare a specimen. Thereafter, according to the conditions of ASTM D1709A, the specimen may be placed in a drop impact tester, and the drop impact strength may be measured by freely dropping a weight having a diameter of 38 mm at a height of 0.66 m.

In the present invention, by controlling the drop impact strength of the encapsulant layer to 1400 g or more, it is possible to protect the photovoltaic cell or the photovoltaic array from external impact, thereby preventing damage to the photovoltaic module.

The photovoltaic module of the present invention to which the characteristic encapsulant is applied as described above may include a wafer-based module or a thin film type module, and may be various types of photovoltaic modules known in the art.

Meanwhile, the photovoltaic module of the present invention is not particularly limited as long as it includes the characteristic encapsulant as described above, and may be configured in various forms. 1 and 2 are diagrams showing cross-sectional views of photovoltaic modules according to various aspects of the invention.

1 is a view illustrating an example of a wafer-based photovoltaic module 10 including an encapsulant of the present invention. As shown in FIG. 1, a photovoltaic module according to an aspect of the present invention typically includes a light receiving substrate 11, which may be composed of a ferroelectric (ex. Glass); A support substrate 13, which may be composed of a tedla or PET / SiOx-PET / Al-based material; Photovoltaic elements (14), such as the silicon wafer; And an encapsulant layer 12 encapsulating the photovoltaic device 14. At this time, the encapsulant layer 12 encapsulates the photovoltaic element 14 and encapsulates the first layer 12a and the photovoltaic element 14 attached to the light receiving substrate 11, while supporting the photovoltaic element 14. ) May comprise a second layer 12b attached thereto. In the present invention, the first layer and the second layer constituting the encapsulant layer 12 may contain the characteristic components as described above.

2 is a cross-sectional view of a thin film photovoltaic module 20 according to another aspect of the present invention. As shown in FIG. 2, in the case of the thin film type photovoltaic module 20, the photovoltaic device 24 may be formed on the light receiving substrate 21, which may be typically composed of a ferroelectric. Such a thin film photovoltaic device 24 can be deposited by conventional methods such as chemical vapor deposition (CVD). 2, the photovoltaic module 20 of FIG. 2 includes an encapsulant layer 22 and a support substrate 23 similarly to the photovoltaic module 10 of FIG. 1, and the encapsulant layer 22 may be formed of a single layer. have. A detailed description of the encapsulant layer 22 and the support substrate 23 is as described above.

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

In the present invention, for example, a composition may be prepared by appropriately blending each of the above-mentioned components for forming an encapsulant, which may be prepared in a hot melt sheet or liquid form, and the photovoltaic module may be manufactured using the composition.

The term "high temperature melt sheet" as used herein refers to a sheet-like molded article made of an encapsulant composition comprising the ethylene-alpha olefin copolymer and the silane-modified ethylene-alpha olefin copolymer described above. The hot melt sheet is present in an uncured or partially cured state prior to application, at room temperature rises in strength and flow resistance, can be converted to a low viscosity flowable material by heating, and can be high viscosity by cooling again. It may be a material. In this field, a method for producing the above-mentioned high temperature meltable sheet using each of the above materials is known.

When the high temperature melt sheet is used in the present invention, the photovoltaic module is manufactured according to a desired module structure by laminating a light receiving substrate, a photovoltaic device, a support substrate, and a high temperature melt sheet, and heating or pressing while vacuum suction. can do.

In addition, in the present invention, the encapsulant composition according to the present invention may be prepared in a liquid form, and the encapsulant may be formed and cured around the photovoltaic device by a coating method using the same to manufacture the photovoltaic module described above. Although not particularly limited, it is preferable to form an encapsulant by a direct coating method using a liquid composition as described above in terms of reduction in manufacturing cost and process efficiency.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.

Manufacturing example  1: ethylene- Alphaolefin  Preparation of Copolymer

In a 1.5 L continuous stirred reactor preheated from 100 ° C. to 150 ° C., 3.20 kg / h of hexane solvent, 0.55 kg / h of 1-octene comonomer and 0.63 kg / h of ethylene monomer in the contents shown in Table 1 below. Was fed at a pressure of 89 bar. 0.40 μM / min of [(7-methyl-1,2,3,4-tetrahydroquinolin-8-yl) tricyclopentadienyl-eta5, kappa-N] titanium methyl and An octadecylmethylammonium tetrakis (pentafluorophenyl) borate cocatalyst of 0.60 μmol / min was fed to the reactor to proceed with the copolymerization reaction. The copolymerization was carried out at a temperature of 140 ℃ to 180 ℃, the polymer solution formed by the copolymerization reaction is reduced to 7bar at the rear end of the reactor, and then sent to a solvent separator preheated to 230 ℃ to transfer most of the solvent by a solvent separation process Removed. The copolymer sent to the second solvent separator by the pump completely removed residual solvent by a vacuum pump, and then passed through cooling water and a cutter to obtain granulated polymer.

Manufacturing example  2: ethylene- Alphaolefin  Preparation of Copolymer

An ethylene-alpha olefin copolymer was prepared in the same manner as in Preparation Example 1, except that contents of the hexane solvent, the 1-octene monomer, and the ethylene monomer were changed as shown in Table 1 below.

Polymerization solvent Ethylene monomer Alphaolefin  Monomer Manufacturing example  One 3.20 kg / h 0.63 kg / h 0.55 kg / h Manufacturing example  2 3.20 kg / h 0.63 kg / h 0.44 kg / h Polymerization Solvent: Hexane
Alphaolefin monomer: 1-octene

Manufacturing example  3: ethylene- Alphaolefin  Copolymer

As the ethylene / 1-octene copolymer, ENGAGE 8452 from Dow chemical company was used.

Manufacturing example  4: ethylene- Alphaolefin  Preparation of Copolymer

An ethylene-alpha olefin copolymer was prepared in the same manner as in Preparation Example 1, except that contents of the hexane solvent, the 1-octene monomer, and the ethylene monomer were changed as shown in Table 2 below.

Polymerization solvent Ethylene monomer Alphaolefin  Monomer Manufacturing example  4 3.20 kg / h 0.63 kg / h 0.40 kg / h Polymerization Solvent: Hexane
Alphaolefin monomer: 1-octene

The physical properties of the ethylene-alpha olefin copolymers of Preparation Examples 1 to 4 were measured by the methods shown below.

(1) density measurement

Density was measured using ASTM D792 analysis.

(2) Dragon Flow index ( MI ) Measure

The melt flow index was measured using ASTM D1238 analysis.

(3) molecular weight distribution ( PDI ) Measure

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene-alphaolefin copolymers prepared in Preparation Examples 1 and 2 were measured using the molecular weight measuring apparatus PL-GPC 220, respectively, The molecular weight distribution was calculated by substituting Equation 4.

[Formula 4]

PDI = Mw / Mn

(4) monomer reactivity ratio measurement

The ethylene-alpha olefin copolymers prepared in Preparation Examples 1 and 2 were added to a solvent (1,1,2,2-tetrachloroethane-d2 (TCE-d2): trichlorobenzene (TCB) = 2: 1, volume ratio). After dissolution, about 0.4 ml of the tube was 5 mm in diameter and 18 cm in length. The tube is then placed on a 13C NMR spectrometer and kee, kec at conditions where the frequency, temperature, decay time and scans of the 13C NMR spectrometer are 150 MHz, 100 ° C., 0.5 seconds to 1 second and 50 k, respectively. , kcc and kce values were measured, and the monomer reactivity ratios were calculated by substituting the same into the following Formulas 5 and 6.

[Formula 5]

Re (reactivity ratio of ethylene monomer) = kee / kec

[Formula 6]

Rc (reactivity ratio of alpha olefin comonomer) = kcc / kce

The measurement results of the physical properties as described above are summarized in Table 3 below.

Basic properties Monomer reactivity ratio Density (g / cm ³ ) MI (g / 10 min ) PDI Re Rc Re  × Rc Manufacturing example  One 0.875 5.1 2.35 1.34 0.74 0.98 Manufacturing example  2 0.886 4.5 2.41 1.32 0.37 0.49 Manufacturing example  3 0.875 3.0 2.50 2.04 0.66 1.34 Manufacturing example  4 0.890 3.0 2.42 1.33 0.40 0.53 MI: melt flow index
PDI: molecular weight distribution
Re: Reactivity Ratio of Ethylene Monomer
Rc: Reactivity ratio of the alphaolefin comonomer

Manufacturing example  5: Silane  Modified Ethylene Alphaolefin  Preparation of Copolymer

The ethylene / 1-octene copolymer prepared in Preparation Example 1 was subjected to 2,5-bis (tert-butylperoxy) in a twin screw extruder (L / D = 40, diameter 27 mm, residence time 1 minute, pressure 23 bar). A vinyl silane-modified ethylene / 1-octene copolymer was prepared by polymerization with a vinyltrimethoxy silane monomer injected into a -2,5-dimethylhexane (Lupersol 101) catalyst mixed phase. The amount of vinyltrimethoxy silane added at this time was 4.5 parts by weight (0.45 kg / h) based on 100 parts by weight of the silane-modified ethylene / 1-octene copolymer, and 2,5-bis (tert-butylper Oxy) -2,5-dimethylhexane (Lupersol 101) catalyst amount was 1/20 of the content of the vinyltrimethoxy silane. In the twin screw extruder, the temperature at which the ethylene / 1-octene copolymer and the vinyltrimethoxy silane were introduced was 50 ° C, the temperature of the reactor portion under nitrogen injection was 210 ° C, and the exit temperature after the reaction was It was 140 degreeC.

Manufacturing example  6: Silane  Modified Ethylene Alphaolefin  Preparation of Copolymer

A vinyl silane-modified ethylene / 1-octene copolymer was prepared in the same manner as in Preparation Example 5, except that the ethylene / 1-octene copolymer prepared in Preparation Example 2 was used as the ethylene-alphaolefin copolymer.

Manufacturing example  7: Silane  Modified Ethylene Alphaolefin  Preparation of Copolymer

Vinyl silane-modified ethylene / in the same manner as in Preparation Example 5, except that the ethylene / 1-octene copolymer (ENGAGE 8452, manufactured by Dow Chemical Company) of Preparation Example 3 was used as the ethylene-alphaolefin copolymer. A 1-octene copolymer was prepared.

Example  One

80 g / min ethylene-alpha olefin copolymer prepared in Preparation Example 1, 20 g / min silane-modified ethylene-alpha olefin copolymer prepared in Preparation Example 5, benzotriazole UV absorber (Cyasorb UV-531) 0.5 0.4 mm thick sheet was prepared by continuously feeding g / min and 0.5 g / min of a hindered amine light stabilizer (Cyasorb THT-6460) into a twin screw extruder (L / D = 40). . Nitrogen was injected into the extruder and the extruder temperature ranged from 80 ° C to 210 ° C.

Example  2

Except that 20 g / min of the ethylene-alpha olefin copolymer prepared in Preparation Example 1 and 20 g / min of the silane-modified ethylene-alpha olefin copolymer prepared in Preparation Example 5 were used. 0.4 mm thick encapsulant sheet was prepared.

Example  3

80 g / min ethylene-alpha olefin copolymer prepared in Preparation Example 2, 20 g / min silane-modified ethylene-alpha olefin copolymer prepared in Preparation Example 6, benzotriazole UV absorber (Cyasorb UV-531) 0.5 0.4 mm thick sheet was prepared by continuously feeding g / min and 0.5 g / min of a hindered amine light stabilizer (Cyasorb THT-6460) into a twin screw extruder (L / D = 40). . Nitrogen was injected into the extruder and the extruder temperature ranged from 80 ° C to 210 ° C.

Example  4

Except that 20 g / min of the ethylene-alpha olefin copolymer prepared in Preparation Example 2 and 20 g / min of the silane-modified ethylene-alpha olefin copolymer prepared in Preparation Example 6 were used. 0.4 mm thick encapsulant sheet was prepared.

Example  5

A 0.4 mm thick encapsulant sheet was prepared in the same manner as in Example 1, except that 10 g / min of the ethylene-alphaolefin copolymer prepared in Preparation Example 4 was further used.

Example  6

A 0.4 mm thick encapsulant sheet was prepared in the same manner as in Example 3, except that 10 g / min of the ethylene-alphaolefin copolymer prepared in Preparation Example 4 was further used.

Comparative example  One

Without adding other additives, a continuous twin-screw extruder (80 g / min ethylene-alpha olefin copolymer prepared in Preparation Example 3 and 20 g / min silane-modified ethylene-alpha olefin copolymer prepared in Preparation Example 7 was continuously Twin screw extruder, L / D = 40) to prepare a 0.4mm thick sheet (sheet). Nitrogen was injected into the extruder, and the extruder temperature was 80 ° C to 210 ° C.

Test Example  One ( Light transmittance and blur ( Hayes ))

The transparency of the encapsulant sheet prepared in Examples 1 to 4 and Comparative Example 1 was measured by using a reflectance-transmittance meter (HR-100, manufactured by Murakami Co., Ltd.) as described below. It measured by calculation.

Light transmittance (%) = 100 × total transmitted light amount / incident light amount

Cloudiness (%) = 100 × diffuse transmitted light amount / total transmitted light amount

Test Example  2 (peel strength)

The encapsulant sheet prepared in Examples 1 to 4 and Comparative Example 1 was cut to a size of 5 cm × 5 cm (width × length). Thereafter, one surface of the encapsulant sheet was attached to a plate glass (thickness: 3 mm), which is a light receiving substrate, and the other surface was attached to a support substrate, and then 15 minutes at a temperature of 150 ° C. in a vacuum laminator for manufacturing a photovoltaic module. The samples were prepared by crimping, and then peel strength was measured using a tensile tester at a temperature of 25 ° C., a peel rate of 50 mm / min, and a peel angle of 90 ° (condition of ASTM D903) at 20 minutes. It was. As the support substrate, a laminated sheet in which a polyvinyl fluoride resin sheet having a thickness of 38 μm, an aluminum foil having a thickness of 30 μm, and a polyvinyl fluoride resin sheet having a thickness of 38 μm was sequentially laminated was used.

Test Example  3 (thermal stability)

Thermal stability of the encapsulant sheet prepared in Examples 1 to 4 and Comparative Example 1 measured the temperature of the 5% weight loss in the thermogravimetric analysis (TGA), according to ASTM G154 conditions.

Test Example  4 (impact resistance)

Specimens were prepared by cutting the encapsulant sheets prepared in Examples 1 to 4 and Comparative Example 1 to a size of 5 cm × 5 cm × 100 μm (width × length × thickness). Thereafter, according to the conditions of ASTM D1709A, the specimen was placed in a drop impact tester, and a drop impact strength was measured by freely dropping a weight having a diameter of 38 mm at a height of 0.66 m.

Test Example  5 (ultraviolet stability)

The encapsulant sheet prepared in Example 1 and Comparative Example 1 was kept in an ultraviolet irradiator (QUV, Q-Lab Co., Ltd.), and the residence time was varied. Thereafter, the yellowness (Yellow Index) of the encapsulant sheet for each residence time was measured by Observer 2 degrees with a C light source using a colorimeter (Colorflex, HunterLab Co., Ltd.) (ASTM D1925). In addition, the elongation of the encapsulant sheet for each residence time was measured according to ASTM D882 conditions.

The light transmittance, haze (haze), peel strength, thermal stability and drop impact strength of Examples 1 to 4 and Comparative Example 1 measured in the same manner as described above are summarized in Table 4 below.

Light transmittance
(%) Cloudy road
(%) Peel strength
(N / 15mm) Thermal stability
(℃) Drop impact strength
(g) Example 1 92.8 6 80 400 1400 Example 2 92.6 7 110 403 1800 Example 3 92.0 10 90 404 1600 Example 4 92.0 11 160 405 1900 Example 5 92.6 7 80 403 2000 Example 6 92.0 11 90 404 2100 Comparative Example 1 91.8 15 50 395 1400

The yellowing and elongation rate by residence time in the ultraviolet irradiator of Example 1 and Comparative Example 1 measured in the same manner as described above are summarized in Table 5 below.

UV irradiation time (hour) 0 50 500 1000 1500 2000 3000 4000 Example 1 Yellowing 2.2 2.4 2.0 2.5 2.6 2.6 2.7 2.8 Elongation (%) 920 850 900 880 850 810 830 800 Comparative Example 1 Yellowing 2.0 2.5 2.2 2.5 2.6 2.8 2.9 3.0 Elongation (%) 910 700 750 640 600 450 320 F F (failed): not measurable

As shown in Table 4, in Examples 1 to 4 according to the present invention, the light transmittance and cloudiness were 92% or more and 14% or less, respectively. The thermal gravimetric analysis (TGA) showed excellent thermal stability with a temperature of 5% weight loss of more than 400 ° C. On the other hand, in Comparative Example 1 not according to the present invention, the light transmittance and haze were 91.8% and 15%, respectively. TGA) had poor thermal stability with a temperature of 5% weight loss of 395 ° C.

In addition, as shown in Table 5, in Example 1 according to the present invention, the elongation rate was 800% or more even when irradiated with UV light for 4000 hours, but in Comparative Example 1, the elongation rate was rapidly decreased as the UV irradiation time was increased. When the ultraviolet rays were irradiated for 4000 hours, the elongation rate could not be measured.

10: wafer-based photovoltaic module 20: thin film photovoltaic module
11, 21: light receiving substrate 12, 22: encapsulant layer
12a, 12b: first layer 13, 23: support substrate
14, 24: photovoltaic device

Claims (17)

Ethylene-alpha olefin copolymer which satisfy | fills following General formula 1; And silane-modified ethylene-alphaolefin copolymers,
An encapsulant composition having a melt flow index (MI) of 0.2 g / 10 min to 50 g / 10 min of an ethylene-alpha olefin copolymer satisfying the following general formula:
Encapsulant Composition:
[Formula 1]
Re × Rc ≤ 1.0
In Formula 1, Re represents kee / kec, Rc represents kcc / kce, and kee represents a growth rate constant when ethylene is added to a growth chain having a terminal active point of ethylene monomer, and kec represents The growth kinetics when the alpha olefin comonomer is added to the growth chain where the terminal active point is ethylene monomer, kcc represents the growth kinetics when the alpha olefin comonomer is added to the growth chain where the terminal active point is alpha olefin comonomer Kce represents a growth rate constant when an ethylene monomer is added to a growth chain whose terminal active point is an alphaolefin comonomer. The method of claim 1,
The encapsulant composition, wherein the ethylene-alpha olefin copolymer has a density of 0.85 g / cm 3 to 0.91 g / cm 3. The method of claim 1,
The molecular weight distribution (Mw / Mn) of the ethylene-alpha olefin copolymer is 1.5 to 3.5. The method of claim 1,
The silane-modified ethylene-olefin copolymer is 10 parts by weight to 900 parts by weight based on 100 parts by weight of the ethylene-alpha olefin copolymer. The method of claim 1,
An encapsulant composition further comprising an ethylene-alpha olefin copolymer having a different molecular weight or density from the ethylene-alpha olefin copolymer. The method of claim 5, wherein
The ethylene-alpha olefin polymer further included is included in the encapsulant composition 10 to 1000 parts by weight based on 100 parts by weight of the encapsulant composition. The method of claim 1,
Ethylene-alpha olefin copolymer is an encapsulation material composition (alternation copolymer). The method of claim 1,
An encapsulant composition further comprising at least one additive selected from the group consisting of UV absorbers, light stabilizers, antioxidants, glass fever, and glass bubbles. An encapsulant comprising the encapsulant composition according to any one of claims 1 to 8. The method of claim 9,
Encapsulant in which the encapsulant is in the form of a sheet or film. 11. The method of claim 10,
An encapsulant having a thickness of 0.2 mm to 0.8 mm. A method for producing an encapsulant, comprising molding the encapsulant composition according to any one of claims 1 to 8 in the form of a sheet or a film. Support substrates;
A photovoltaic cell or photovoltaic array formed on the support substrate;
A light receiving substrate formed on the photovoltaic cell or photovoltaic array; And
A photovoltaic module which encapsulates the photovoltaic cell or photovoltaic array between the support substrate and the light receiving substrate, and has an encapsulant layer comprising the encapsulant composition according to any one of claims 1 to 8. The method of claim 13,
The encapsulant layer is a single layer;
A multilayer photovoltaic module comprising a first layer encapsulating a photovoltaic cell or photovoltaic array in contact with a light receiving substrate and a second layer encapsulating the photovoltaic cell or photovoltaic array in contact with a support substrate. The method of claim 13,
The light transmittance of the encapsulant layer is 92% or more. The method of claim 13,
Photovoltaic module with a cloudiness of encapsulant layer of 14% or less. The method of claim 13,
The photovoltaic module having a peel strength of the encapsulant layer of 60 N / 15 mm or more.

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