KR101367505B1 - Encapsulant - Google Patents

Abstract

The present invention relates to a filler. The filler of the present invention can be effectively applied to various optoelectronic devices, for example.

Description

Filler {ENCAPSULANT}

The present invention relates to a filler.

The filling material encapsulates a light emitting portion or a light detecting portion in an optoelectronic device such as a photovoltaic cell, an LED (Light Emitting Diode) or an OLED (Organic Light Emitting Diode) Can be used.

For example, a lamination method in which a solar cell module is usually laminated according to a desired structure such as a transparent front substrate, a filler, a photovoltaic element material, a back sheet, and the like, and vacuum-squeezed the produced laminate is vacuum-laminated. (lamination method) and the like.

EVA (ethylene-vinyl acetate) resin is most widely used as a filler used in a solar cell module in terms of processability, workability and cost.

However, the EVA resin is contained in an optoelectronic device such as a front substrate or a backsheet, and has a low bonding strength with an element in contact with the filler. Therefore, when the optoelectronic device is exposed to the outside for a long time, there is a problem that peeling easily occurs between the layers. Further, the EVA resin is pyrolyzed in a heat pressing process or the like to generate toxic gas such as acetic acid gas. Such toxic gases deteriorate the working environment, adversely affect the photovoltaic elements or electrodes contained in the module, deteriorate the module and lower the power generation efficiency.

An object of the present invention is to provide a filler.

The present invention includes an olefin resin having a hydrolyzable group or a reactive group which is a hydrolyzate of the hydrolyzable group, and measured after being pressed and bonded to a glass substrate for 10 minutes using a vacuum laminator at a temperature of 150 ° C. It relates to a filler having a peel force of 70 N / 15 mm or more.

Hereinafter, the filler of the present invention will be described more specifically.

In one example, the filler may be used to encapsulate devices included in optoelectronic devices, such as photovoltaic cells, LEDs or OLEDs. However, the use to which the filler of the present invention is applied is not limited to the above.

The filler may be prepared using a composition comprising an olefin resin in which a hydrolyzable group is introduced into the main chain, the side chain, or the terminal, or a monomer having a hydrolyzable group is grafted. In the above, the olefin resin means a polymer comprising at least one olefin as polymerized units, wherein the polymer is a homopolymer which is a homogeneous polymer made from a single monomer; And copolymers comprising chemically different segments or blocks, whether produced by the reaction of two or more different monomers or formed from a single monomer. In addition, in this specification, the olefin resin in which the hydrolysable group is introduce | transduced as mentioned above can be called "modified olefin resin."

In the present invention, the hydrolyzable group introduced into the olefin resin may be hydrolyzed in a process of preparing a filler using the resin composition as described above, or a process of applying the prepared filler to a device, and may be converted into a reactive group. The term "reactive group" in the present invention, when the filler of the present invention is applied to the optoelectronic device, can be in physical or chemical interaction with the functional groups present in the contact surface of the filler of the element of the optoelectronic device that the filler is in direct contact. It means functional group. For example, a glass substrate is a representative element in direct contact when a filler is applied to an optoelectronic device. In this case, when the reactive functional group is a hydroxy group, a physical bond such as a hydroxy group and a hydrogen bond, which are functional groups also present on the glass substrate; Or a chemical covalent bond through a condensation reaction or the like, thereby improving the adhesion.

In the present invention, the filler includes the olefin resin as described above, while the filler exhibits excellent adhesion to various elements, while maintaining other necessary physical properties.

Specifically, the filler may have a peel force of at least 70 N / 15 mm, preferably at least 100 N / 15 mm, more preferably at least 120 N / 15 mm, more preferably at least 160 N / 15 mm to the glass substrate. The said peeling force is a 90 degree peeling force measured after crimping | bonding and bonding said filler to a glass substrate using a vacuum laminator, and it is a peeling force measured according to the method in the Example mentioned later specifically ,. In the above, the upper limit of the numerical value of the peel force is not particularly limited, and can be adjusted, for example, at 300 N / 15 mm or less.

In the present invention, in the manufacturing or application process of the filler, the peeling force as described above is achieved by controlling the degree of hydrolysis of the hydrolyzable group of the olefin resin and introducing a suitable crosslinked structure into the filler. can do.

For example, the filler of the present invention can satisfy the conditions of the following general formulas (1) and (2).

[Formula 1]

H = A / B = 0.01 to 1.5

[Formula 2]

R = C / B = 0.01 to 1.5

In Formulas 1 and 2, H represents a hydrolyzable group index, and A represents intensity of a peak derived from the hydrolyzable group when Fourier Transform Infrared Spectrometry (FT-IR) analysis is performed on the filler. ), B represents the intensity of the peak observed at 720 cm ⁻¹ in the FT-IR analysis, R represents the reactive group index, and C represents the peak derived from the reactive group in the FT-IR measurement. Indicates the strength of

The FT-IR analysis above is performed in the manner described in the Examples below. In addition, numerical value A is the intensity | strength of the peak observed at the time of FT-IR analysis according to the kind of hydrolysable group introduce | transduced into an olefin resin, and the specific position of the peak can be determined according to the specific kind of hydrolysable group. . In addition, the said numerical value C is intensity | strength of the peak observed at the time of FT-IR analysis according to the kind of reactive group which the hydrolyzable group introduce | transduced into an olefin resin is produced | generated by hydrolysis, and the specific position of the peak is It may be determined according to a specific kind. In addition, the peak observed at 720 cm ^-1 in the FT-IR analysis is a peak induced due to the rocking motion of all -CH ₂ -of the resin, and the intensity (C) of the peak is a reference value ( reference value).

In Formula 1, H may be preferably 0.05 to 0.5, more preferably 0.05 to 0.3. In addition, in Formula 2, R may be preferably 0.03 to 0.5, more preferably 0.03 to 0.1.

Within the range as described above, the filler exhibits high peeling force and can also maintain excellent other required physical properties.

The kind of hydrolyzable group contained in the olefin resin of the said filler is. It is not particularly limited. For example, the hydrolyzable group may be a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group or an alkylenoxythio group. In this case, examples of the halogen atom include chlorine (Cl). Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, Examples of the aryloxy group include an aryloxy group having 6 to 18 carbon atoms and a carbon number of 6 to 12, and may be, for example, phenoxy. Examples of the acyloxy group include an acyloxy group having 1 to 12 carbon atoms, Examples of alkylthio groups include alkylthio groups having 1 to 12 carbon atoms, and examples of alkyleneoxy groups include alkyleneoxy groups having 1 to 12 carbon atoms. The hydrolyzable group may preferably be alkoxy, for example, an alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and specifically, a methoxy group and an ethoxy group. It may be a time period, a propoxy group, an isopropoxy group or a butoxy group, Preferably it may be a methoxy group or an ethoxy group. In addition, the kind of the reactive group is determined by the kind of the hydrolyzable group to be used, and is not particularly limited. For example, the reactive group is preferably a hydroxy group.

The kind of the olefin resin which can provide the above hydrolyzable group to the filler is not particularly limited. For example, the resin may be a silane-modified olefin resin. The olefin resin as described above may be, for example, copolymerizing α-olefin and a silane compound having a site and a hydrolyzable group copolymerizable with the α-olefin simultaneously or stepwise, or an unsaturated silane compound having a hydrolyzable group. Can be prepared by grafting to an olefin resin.

Specifically, the olefin resin, for example, a copolymer comprising an α-olefin and an unsaturated silane compound represented by the following formula (1) in copolymerized form; Alternatively, the olefin resin may be a graft polymer grafted with an unsaturated silane compound represented by Formula 1 below.

[Formula 1]

DSi (X) _m Y _(3-m)

In Formula 1, D represents alkenyl bonded to a silicon atom, X represents a hydrolyzable group or a hydrolyzate thereof bonded to a silicon atom, Y represents a non-hydrolyzable group bonded to a silicon atom, and m Represents an integer of 1 to 3.

In Formula 1, the alkenyl group may be, for example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group, or the like, and preferably a vinyl group. have.

In addition, in Formula 1, the specific kind of X may be a hydrolyzable group or a hydrolyzate thereof as described above.

Examples of the nonhydrolyzable moiety of the above formula (1) include hydrogen, an alkyl group, an aryl group or an aralkyl group. In the above, the alkyl group may be, for example, an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. The aryl group in Y may be an aryl group having 6 to 12 carbon atoms, for example, a phenyl group, and the aralkyl group may be an aralkyl group having 7 to 12 carbon atoms, for example, a benzyl group.

In Formula 1, m is an integer of 1 to 3, preferably 3.

Specific examples of the unsaturated silane compound of Formula 1 are not particularly limited, and may be a general silane compound known in the art as having a hydrolyzable group to be introduced into an olefin resin. For example, when introducing an alkoxy group into a olefin resin as a hydrolyzable group, the said silane compound is vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, and vinyl tree. Butoxy silane or vinyltripentoxy silane, and the like, of which vinyltrimethoxy silane or vinyltriethoxy silane is preferred, but is not limited thereto.

In addition, examples of the α-olefin included in the copolymerized form of the olefin resin or included in the grafted olefin resin include ethylene, propylene, 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene , 3-methyl-1-butene, 1-hexene, 1-heptane, 1-octene, 1-nonene or 1-decene may be one kind or two or more, and the olefin resin is a polymerized α-olefin as described above The resin may be included in the form, but is not limited thereto.

In the olefin resin of the present invention, the above-mentioned unsaturated silane compound is preferably used in an amount of 0.1 to 10.0 parts by weight based on 100 parts by weight of the? -Olefin in the case of the graft polymer relative to 100 parts by weight of the olefin resin 0.5 part by weight to 5.0 parts by weight. Unless otherwise specified, unit weight parts herein means weight ratios. In this range, the adhesiveness of the filler, for example, adhesion to a glass substrate and the like can be kept excellent.

In the present invention, the olefin resin may be preferably a graft polymer obtained by grafting an unsaturated silane compound of Formula 1 to an olefin resin, in which case the olefin resin may be polyethylene. The term " polyethylene " includes not only a homopolymer of ethylene but also at least 50 mol% or more of ethylene as a polymerization unit, and also includes an? -Olefin having three or more carbon atoms or other comonomers Copolymers may also be included. The polyethylene may be, for example, one or more of low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, ultralow low density polyethylene or linear low density polyethylene.

In the present invention, it is preferable to use polyethylene having many side chains as the unsaturated silane compound grafted. In the case of polyethylene having many side chains, grafting can be performed more efficiently. Typically, polyethylene having a large number of side chains has a low density and a polyethylene having a small number of side chains has a high density. Therefore, in the present invention, it preferred to use a polyethylene of low density and, specifically, a density of 0.85 g / cm ³ to 0.96 g / cm ^3, preferably a density of about 0.85 g / cm ³ to 0.92 g / cm ³ Polyethylene can be used.

The polyethylene has a melt flow rate (MFR) at 190 占 폚 of about 0.1 g / 10 min to about 50 g / 10 min, preferably about 1.0 g / 10 min to 50.0 g / 10 min, About 1.0 g / 10 min to 30.0 g / 10 min. When having the MFR in this range, the filler of the present invention can exhibit excellent moldability and adhesion.

The filler of the present invention may further include a hydrolysis catalyst from the viewpoint of appropriately controlling the hydrolysis of the hydrolyzable group of the olefin resin. The type of hydrolysis catalyst that can be used in the present invention is not particularly limited, and conventional organometallic catalysts or basic hydrolysis catalysts and the like known in the art may be used. In this invention, it is especially preferable to use a basic hydrolysis catalyst. A basic hydrolysis catalyst has an advantage that, compared to other hydrolysis catalysts, while effectively controlling the degree of hydrolysis, it does not impair the physical properties of other additives of the filler.

The specific kind of the basic hydrolysis catalyst is not particularly limited, and examples thereof include organic amine compounds, heterocyclic compounds having nitrogen atoms as ring constituent atoms, metal hydroxides or metal amides, or the like. The above is mentioned. Examples of the organic amine compound may include alkylamine or dialkylamine, and specifically, alkylamine or 2 to 24 carbon atoms having an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group of 2 to 16 carbon atoms or 2 to 8 carbon atoms may be mentioned dialkylamine, and more specifically, ethylamine, hexylamine, n-propylamine or dibutylamine. The heterocyclic compound described above is a hydrocarbon ring compound containing nitrogen as a ring-constituting hetero atom, and specific examples thereof include pyridine. In addition, examples of the metal hydroxide is an example of NaOH, KOH, RbOH, or and the like CsOH, metal amide, NaNH _2, KNH _2, RbNH but are ₂ or CsNH ₂ or the like, without being limited thereto. In the present invention, preferably, an organic amine compound in the catalyst, preferably an alkyl amine or a dialkyl amine, more preferably an alkyl amine having an alkyl group having 1 to 20 carbon atoms or a dialkyl amine having an alkyl group having 2 to 40 carbon atoms Can be used.

In the filler of the present invention, the content of the hydrolysis catalyst is not particularly limited, and may be included, for example, in an amount of 0.01 parts by weight to 2 parts by weight based on 100 parts by weight of the modified olefin resin. However, the content of the catalyst can be appropriately controlled according to the degree of hydrolysis desired or the kind of catalyst.

The filler of the present invention may further include one or more kinds of additives selected from light stabilizers, UV absorbers, heat stabilizers and the like as necessary.

The light stabilizer can serve to prevent photooxidation by capturing the active species of initiation of photo-initiation of the olefin resin, depending on the application to which the filler of the present invention is applied. The type of light stabilizer that can be used in the present invention is not particularly limited, and for example, known compounds such as hindered amine compounds or hindered piperidine compounds may be used.

The UV absorbent absorbs ultraviolet rays from sunlight or the like to convert it into harmless heat energy in the molecule to prevent excitation of the active species of photo-induced initiation in the olefin resin, depending on the use of the filler . The specific kind of UV absorber that can be used in the present invention is not particularly limited and includes, for example, benzophenone, benzotriazole, acrylonitrile, metal complex salt, hindered amine, ultrafine titanium oxide, Inorganic UV absorbers and the like, or a mixture of two or more of them may be used.

Examples of the thermal stabilizer that can be used include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1- dimethylethyl) -6- methylphenyl] (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diyl bisphosphonate and bis (2,4-di-tert- butylphenyl) pentaerythritol dioxide Phosphorus thermal stabilizers such as spits; Hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, and the like.

In the filler of the present invention, the content of the light stabilizer, UV absorber and / or heat stabilizer is not particularly limited. That is, the content of the additive may be appropriately selected in consideration of the use of the filler, the shape or density of the additive, etc., and may be appropriately adjusted within the range of 0.01 wt% to 5 wt% in the filler.

The filler, in addition to the above components, may further appropriately include various additives known in each relevant field, depending on the use.

In the present invention, the shape of the filler as described above is not particularly limited, and may be, for example, sheet or film shape. In this case, the film thickness of the filler can be adjusted to about 10 μm to 2,000 μm, preferably about 100 μm to 1250 μm, in consideration of support efficiency and possibility of breakage, weight reduction or workability of the device, and the like. However, the film thickness of the filler material may be changed depending on the specific application to be applied.

The method for producing the filler in the present invention is not particularly limited. For example, the filler may be prepared by preparing a composition comprising an olefin resin into which a hydrolyzable group is introduced in a reactor; And molding the composition into a film or sheet form.

The method for producing the olefin resin into which the hydrolyzable group is introduced in the reactor is not particularly limited. For example, the said olefin resin mixes (alpha) -olefin, the unsaturated silane compound as mentioned above, and another copolymerizable monomer in the heat-melted state in the reactor as needed, and suitable radical polymerization under predetermined temperature and pressure. It can be prepared by copolymerization simultaneously or stepwise in the presence of an initiator, a chain transfer agent, if necessary. The olefin resin may be prepared by mixing the olefin resin and the unsaturated silane compound as described above in a heated molten state and grafting the unsaturated silane compound to the olefin resin in the presence of a suitable radical generator It is possible.

In one example, a method for preparing a composition comprising the olefin resin comprises: mixing an olefin resin, the silane compound of Formula 1 and a radical generator in a reactor, and grafting the silane compound to an olefin resin; And introducing a hydrolysis catalyst into the same reactor, and mixing the same.

The type of the reactor in which the olefin resin is produced is not particularly limited as long as it can produce a desired resin by reacting reactants in a heat-fused or liquid state. For example, the reactor may be a cylinder with an extruder or a hopper. In the case of using such a reactor, for example, a liquid silane compound and a radical generator are added to an olefin resin heated and melted through an extruder and extruded, or an olefin resin, a radical generator and a silane compound are mixed in a hopper After the addition, the olefin resin can be produced by heating and melting in a cylinder and reacting.

In the above method, the hydrolysis catalyst may be introduced before or after the olefin resin is formed into the reactor in which the olefin resin is prepared as described above. In this case, the hydrolysis catalyst may be added to the reactor in which the ultraviolet absorbent, heat stabilizer, And other additives may be added together. Thus, by simultaneously producing the olefin resin and mixing with the additive in one reactor, the process can be simplified.

The hydrolysis catalyst and / or other additives may be introduced into the reactor as it is, or may be added in the form of a master batch and mixed. In the above, the master batch refers to a pellet-shaped raw material in which the additives to be added are concentrated and dispersed at a high concentration, and in particular, in processing and molding plastic raw materials by extrusion or injection method, a specific function is applied to the finished product. Used to introduce additives.

The method for introducing an additive such as a hydrolysis catalyst into the reactor in which the olefin resin is formed is not particularly limited. For example, a side feeder may be installed at an appropriate position of the extruder or the cylinder, A method of adding an additive in the form of a master batch, or a method of mixing the mixture with an olefin resin or the like in a hopper and inputting the mixture.

In the above method, the conditions such as the specific kind and design of the reactor, the heating and melting, the mixing or the reaction and the conditions such as the time and the kind, the kind of the radical generator and the production method of the master batch are not particularly limited, Can be appropriately selected.

There is no particular limitation on the method of molding the obtained composition into a sheet or film after the above-mentioned process. For example, a conventional filming or sheeting process such as a T-die process or extrusion may be used.

In the above method, preferably, the above-described manufacturing process of the resin composition and the sheeting or filming process can be carried out in an in-situ process in a device connected to each other.

The invention also relates to an optoelectronic device comprising an optoelectronic device encapsulated by the filler described above.

The optoelectronic device may be, for example, a light emitting or photosensitive site such as a photovoltaic cell, an LED, or an OLED.

In the present invention, the specific structure of the optoelectronic device or the method for encapsulating the optoelectronic device using the filler of the present invention is not particularly limited, and the method and structure commonly applied in the field may be applied according to the device.

For example, when the optoelectronic device is a photovoltaic cell in the present invention, the optoelectronic device, as shown in Fig. 1 or 2, the light receiving substrates 11 and 21, the back sheet 12 and 22 and the light receiving substrate 11 , 21 and a solar cell comprising photovoltaic elements 13, 23 encapsulated by fillers 14 (a), 14 (b), 24 according to the invention between the back sheets 12, 22. It may be a module (1, 2).

The specific types of the light receiving substrate, the back sheet, and the photovoltaic device are not particularly limited. For example, the light receiving substrate may be a conventional plate glass; Or a transparent composite sheet obtained by laminating a glass, a fluororesin sheet, a weather resistant film and a barrier film, and the back sheet may be a composite sheet comprising a metal such as aluminum, a fluororesin sheet, a weather resistant film and a barrier film. In addition, the photovoltaic device may be, for example, a thin film photovoltaic device formed by a silicon wafer series photovoltaic device or chemical vapor deposition (CVD).

In the present invention, the above-described optoelectronic device may be manufactured by, for example, producing a laminate using a substrate, an optoelectronic device, and a filler of the present invention; And it can be produced by a method comprising the step of heat compression while vacuum suction the prepared laminate.

In the present invention, the method of manufacturing the laminate using the substrate, the optoelectronic device and the filler and the stacking order of each layer in the laminate are not particularly limited, and in view of the structure of the desired optoelectronic device, You may use the method normally applied. In addition, the method of the above-mentioned hot pressing process is not particularly limited, and an appropriate method according to the optoelectronic device can be selected.

For example, the above-described solar cell module can be manufactured by laminating a light receiving substrate, a filler, a photovoltaic element, a back sheet and the like in accordance with a desired structure, followed by heating and pressing while vacuuming the same.

In addition, the conditions of the heat compression process in the above, can be carried out for 5 minutes to 60 minutes, preferably 8 minutes to 40 minutes at a temperature of 90 ℃ to 230 ℃, preferably 110 ℃ to 190 ℃.

The filler of the present invention can be effectively used, for example, as a filler material for various optoelectronic devices.

1 and 2 are cross-sectional views illustrating a solar cell module which is an optoelectronic device according to one example of the present invention.

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.

Example 1

Manufacture of fillers

98 parts by weight of polyethylene having a density of 0.880 g / cm ³ and an MFR of 5 g / 10 minutes at 190 캜, 2 parts by weight of vinyltrimethoxysilane and 0.1 part by weight of a radical generator (dicumyl peroxide) were mixed in an extruder , And the mixture was heated and melt stirred at 200 DEG C to graft the vinyltrimethoxysilane onto the polyethylene. Further, 100 parts by weight of a linear low density polyethylene having a density of 0.870 g / cm ³ , 4 parts by weight of a hindered amine light stabilizer, 2 parts by weight of a benzophenone ultraviolet absorber, 2 parts by weight of a phosphorus- 1 part by weight of dodecylamine (C ₁₂ H ₂₅ NH ₂ ) was melted and processed into a pelletized master batch was fed into the extruder at a rate of about 5 to 10 parts by weight using a side feeder to prepare a vinyl trimethoxysilane Were mixed with the grafted polyethylene to prepare a resin composition. Subsequently, the resin composition was fed into a side hopper of a film forming machine having a twin-screw extruder (27 mm) and a T die (width: 500 mm) and processed at an extrusion temperature of 200 캜 and a take-off speed of 3 m / In-sheet filler was processed.

Manufacture of photovoltaic modules

(Thickness: 38 μm), an aluminum foil (thickness: 30 μm), and a polyimide film (thickness: 30 μm) having a thickness of about 3 mm, a filler material, a crystalline silicon wafer, Laminated sheet of a vinyl fluoride sheet (thickness: 38 mu m) were laminated in this order and pressed in a vacuum laminator at 150 DEG C for 15 minutes to produce a photovoltaic module.

Example 2

A filler and a module were prepared in the same manner as in Example 1 except that 1 part by weight of butylamine (C ₄ H ₉ NH ₂ ) was used as a hydrolysis catalyst in the preparation of the masterbatch.

Comparative Example 1

A filler and a photovoltaic module were prepared in the same manner as in Example 1, except that no hydrolysis catalyst was used in the preparation of the masterbatch.

<Measurement of properties>

1. FT-IR analysis

FT-IR analysis was performed on the prepared filler using an FT-IR analyzer (FTS 3000, BIO-RAD). The peak derived from the stretching motion of the methoxy group of methoxysilyl (Si-OCH ₃ ), which is a hydrolyzable group introduced into the olefin resin, was observed at 1091 cm ^-1 in the spectrum derived after the analysis, and the hydrolyzable group was hydrolyzed A peak due to the stretching motion of the hydroxy group of the resulting reactive group (Si-OH) was observed at 3645 cm ^-1 . Accordingly, by substituting the intensity of the peak observed in the intensity of the peak 1091 (intensity) observed in cm ^-1, 720 cm-1 peak intensity, and 3645 cm ^-1 as measured in the in the general formula 1 and 2, respectively , Hydrolyzable group and reactive group index were determined.

[Formula 1]

Hydrolyzable group index = (peak intensity at 1091 cm ^-1 ) / (peak intensity at 720 cm ^-1 )

[Formula 2]

Reactive group index = (peak intensity at 3645 cm ^-1 ) / (peak intensity at 720 cm ^-1 )

2. Measurement of peel strength

The specimens were prepared by cutting the prepared filler to 15 m × 200 m (width × length). Subsequently, the test piece was bonded to a plate glass used as a front substrate of a photovoltaic module for 10 minutes under a condition of 150 mm in a vacuum laminator (manufactured by Meier (trade name: ICOLAM)). Thereafter, using the tensile tester (Lloyd, trade name: LEPlus), the adhered filler was peeled off at a peeling speed of 50 mm / min and a peel angle of 90 degrees, and the peel force was measured.

3. Measurement of gel fraction

The prepared filler was cut into a size of 10 mm × 10 mm (width × length) to prepare a test piece. Thereafter, the specimen was held in hot water at 90 DEG C for 18 hours to gel, and the gel fraction of the filler was measured according to the content specified in ASTM D-2765.

The results of the analysis are summarized in Table 1 below.

Peel strength
(N / 15mm) Gel fraction
(weight%) Reactive factor index Hydrolyzable group index Example 1 0.08 0.12 210 44 Example 2 0.05 0.16 180 27 Comparative Example 1 0.00 0.20 50 2

1, 2: solar cell module 11, 21: light receiving substrate
12, 22: photovoltaic element 13, 23: back sheet
14 (a), 14 (b), 24: filler

Claims (16)

90 degree peeling force measured after bonding to olefin resin which has a hydrolyzable group or the reactive group which is a hydrolyzate of the said hydrolysable group, and adhere | attached and adhered to a glass substrate for 10 minutes at 150 degreeC conditions using a vacuum laminator group is 70 Filler more than N / 15mm. The filler according to claim 1, wherein the peeling force of 90 degrees is 100 N / 15 mm or more. The filler according to claim 1, wherein the hydrolyzable group is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group or an alkyleneoxythio group. The filler according to claim 1, wherein the hydrolyzable group is an alkoxy group having 1 to 12 carbon atoms. The filler according to claim 1, wherein the reactive group is a hydroxy group. The method of claim 1, wherein the olefin resin is a copolymer comprising an α-olefin and an unsaturated silane compound of formula (1) in copolymerized form; Or a graft polymer grafted with an unsaturated silane compound of formula 1 to an olefin resin:
[Chemical Formula 1]
DSi (X) _m Y _(3-m)
In Formula 1, D represents alkenyl bonded to a silicon atom, X is bonded to a silicon atom, and a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group or an alkyleneoxythio group Or represents a hydrolyzate of any of the above, Y is hydrogen, an alkyl group, an aryl group or an aralkyl group which is bonded to a silicon atom, and m represents an integer of 1 to 3. The filler of claim 1 wherein the olefin resin is a graft polymer grafted with an unsaturated silane compound of formula (1) to polyethylene:
[Chemical Formula 1]
DSi (X) _m Y _(3-m)
Wherein D, X, Y and m are as defined in claim 6. The filler according to claim 7, wherein the polyethylene has a density of 0.85 g / cm ³ to 0.96 g / cm ³ . 8. The filler of claim 7, wherein the polyethylene has an MFR of from 0.1 g / 10 minutes to 50 g / 10 minutes at 190 ° C. The filler of claim 1, further comprising a hydrolysis catalyst. The filler according to claim 10, wherein the hydrolysis catalyst is a basic hydrolysis catalyst. The filler according to claim 11, wherein the basic hydrolysis catalyst is an organic amine compound, a heterocyclic compound containing a nitrogen atom as a ring constituent atom, a metal hydroxide or a metal amide. The filler according to claim 11, wherein the basic hydrolysis catalyst is an alkylamine or a dialkylamine. The filler of claim 1, further comprising a light stabilizer, an ultraviolet absorber or a heat stabilizer. delete delete

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