KR20160068259A

KR20160068259A - Olefin resin composition

Info

Publication number: KR20160068259A
Application number: KR1020140173718A
Authority: KR
Inventors: 최성호; 이충훈; 우지윤; 김효주; 공진삼
Original assignee: 주식회사 엘지화학
Priority date: 2014-12-05
Filing date: 2014-12-05
Publication date: 2016-06-15

Abstract

The present invention relates to an olefin resin composition, an encapsulant for photoelectronic devices, a photoelectronic device comprising the encapsulant, and a method for producing an encapsulant for the photoelectronic devices. According to the present invention, it is possible to provide an encapsulant which exhibits excellent long-term storability and superior adhesiveness between a front side substrate and a rear side sheet included in various photoelectronic devices.

Description

OLEFIN RESIN COMPOSITION [0001]

The present application relates to an olefin resin composition, an encapsulant for an optoelectronic device, an optoelectronic device including the encapsulant, and a method for producing the encapsulant for the optoelectronic device.

BACKGROUND ART An optoelectronic device such as a photovoltaic cell, a light emitting diode (LED), or an organic light emitting diode (OLED) is an encapsulant for encapsulating a light emitting or photo- Encapsulant).

For example, a solar cell module is typically manufactured by laminating a transparent front substrate, a sealing material, a photovoltaic element, a sealing material, and a back sheet, which are light receiving substrates, .

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

However, the EVA resin is contained in the optoelectronic device, such as the front substrate or the backsheet, and has a low bonding strength to an element which contacts the sealing material. Therefore, when the module is exposed for a long period of time outdoors, there is a problem that interlayer delamination easily occurs. Further, in the process of manufacturing a solar cell module using an encapsulating material containing an EVA resin, the EVA resin may be thermally decomposed depending on the heating and pressing conditions, and acetic acid gas or the like may be generated. Such acetic acid gas not only deteriorates the working environment but also adversely affects the photovoltaic device or the electrode included in the solar cell module, and also causes deterioration of the module and deterioration of the power generation efficiency.

On the other hand, a copolymer of vinyltrimethoxysilane and ethylene /? - olefin has been used as an encapsulating material for an optoelectronic device having an improved long-term adhesive property in place of the EVA resin. However, since the copolymer of vinyltrimethoxysilane and ethylene /? - olefin is rapidly denatured at room temperature, it must be used immediately after production, thereby increasing the shelf life, It is necessary to develop an excellent sealing material.

Embodiments of the present application provide olefin resin compositions, encapsulants for optoelectronic devices, optoelectronic devices including the encapsulants, and methods of making the encapsulants for optoelectronic devices.

One embodiment of the present application provides an olefin resin composition, which can produce an encapsulant for an optoelectronic device having a slow denaturation rate at room temperature.

The term " aminosilane-modified olefin resin " and " aminosilane-modified ethylene / alpha -olefin copolymer " in the present specification mean that the unsaturated silane compound contains a moiety in which the hydrocarbon group of some silyl group of the grafted olefin resin is converted to a hydroxyl group, But also a moiety having an amine functional group. In order to distinguish the aminosilane-modified olefin resin or the aminosilane-modified ethylene /? - olefin copolymer from the aminosilane-modified olefin resin as described above, the ethylene /? - olefin copolymer grafted only with the unsaturated silane compound without the presence of the aminosilane compound is referred to as " Quot; or " silane-modified ethylene / alpha -olefin copolymer ". The aminosilane-modified olefin resin and the silane-modified olefin resin are collectively referred to as " modified olefin resin ".

The olefin resin composition according to one embodiment of the present application comprises an olefin resin, an unsaturated silane compound, and a radical initiator.

The olefin resin is not particularly limited as long as it is a resin that can be classified as olefin, and examples thereof include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-butene, 4-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-butene, Hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl- Or? -Olefins such as vinyl cyclohexane; Dienes such as 1,3-butadiene, 1,4-butadiene and 1,5-hexadiene; Hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene or 3,4- Halogen-substituted? -Olefins such as butene; Cyclic olefins such as cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene or 5-benzylnorbornene. Homopolymers or copolymers of olefinic monomers of a species or more.

In addition, the olefin resin includes all of the polymers having different configurations of the array even though they are prepared from the monomer (s) having the same composition. For example, in embodiments of the present application, in order to suitably control the viscosity or physical properties of the resin composition depending on the application, the arrangement of the copolymer included in the olefin resin may be randomly, crosswise, blockwise, Can be adjusted.

In embodiments of the present application, the olefin resin may be an ethylene / alpha-olefin copolymer, an ethylene polymer, a propylene polymer or an ethylene-vinyl acetate copolymer, and in one embodiment may be an ethylene / alpha -olefin copolymer have.

The above-mentioned " ethylene / alpha -olefin copolymer " means a polyolefin containing ethylene and an alpha -olefin in a polymerized form as a main component. Specifically, at least 50 mol% of ethylene is polymerized As a polymerization unit, an olefin monomer having three or more carbon atoms, or other comonomers, as a polymerization unit.

The ethylene /? - olefin copolymer may be, for example, a low density ethylene /? - olefin copolymer, a medium density ethylene /? - olefin copolymer, a high density ethylene /? - olefin copolymer, an ultra low density ethylene / , Ultra-low density ethylene /? - olefin copolymer, and linear low density ethylene /? - olefin copolymer, may be used alone or in combination of two or more.

The ethylene /? - olefin copolymer having a large number of side chains generally has a low density and a low side chain, and the ethylene /? - olefin copolymer generally has a high density. In addition, the more side chains, the higher the efficiency of grafting. Accordingly, in one embodiment of the present application, an olefin resin grafted with an unsaturated silane compound and / or an aminosilane compound can be used with a low density ethylene /? - olefin copolymer having many side chains, thereby enhancing grafting efficiency The adhesive force of the sealing material can be improved.

Accordingly, embodiments of the present application specifically include a density of about 0.85 g / cm ³ to 0.96 g / cm ³ , such as a density of about 0.85 g / cm ³ to 0.92 g / cm ³ , 0.86 g / cm ³ ³ to ^{0.91 g / cm 3, 0.87 g} / cm 3 to ^{0.90 g / cm 3, 0.88 g} / cm 3 to 0.91 g / cm ³ or 0.87 g / cm ³ to 0.905 g / cm ³ of ethylene / α- olefin Coalescence may be used, but is not limited thereto.

The ethylene /? - olefin copolymer may have a melt flow rate (MFR) of about 1.0 g / 10 min to about 50.0 g / 10 min, a melt flow rate of about 1.0 g / 10 min 10.0 g / 10 min, about 1.0 g / 10 min to 8.0 g / 10 min, or about 3.0 g / 10 min to 7.0 g / 10 min. When the MFR is in this range, for example, the olefin resin has a low molecular weight, so that the olefin resin composition can exhibit excellent moldability and the like. Such MFR (melt flow rate) can be measured, for example, under a load of 2.16 kg at 190 캜 for an ethylene /? - olefin copolymer, but is not limited thereto.

As the unsaturated silane compound contained in the olefin resin composition, vinyltriethoxysilane can be used in particular. The vinyltriethoxysilane is added to the olefin resin in the presence of a radical initiator or the like, Grafted to the backbone containing the silane-modified olefin resin or the aminosilane-modified olefin resin. That is, the olefin resin composition of the present application can provide a graft polymer in which the vinyltriethoxysilane is grafted to an olefin resin. The encapsulating material comprising the copolymer grafted with vinyltriethoxysilane to the olefin resin may have a slow modifying rate at room temperature, and accordingly, the present application can provide an encapsulating material having excellent long-term storage property .

In one example, the olefin resin composition may include 0.1 to 10.0 parts by weight, 0.5 to 7.0 parts by weight, and 1.0 to 5.5 parts by weight of the vinyltriethoxysilane based on 100 parts by weight of the solid content of the total olefin resin composition Or 0.5 to 5.0 parts by weight. Within such a range, it is possible to provide an encapsulating material which can maintain the adhesiveness of the copolymer, for example, adhesion to a glass substrate, a backsheet, and the like with excellent long-term storage properties.

Unless otherwise specified, unit weight parts in the present specification means weight ratios.

In one example, the olefin resin composition may further comprise an aminosilane compound. The aminosilane compound is used in grafting denaturation step of an olefin resin, for example, an ethylene / alpha -olefin copolymer And functions as a catalyst for promoting the hydrolysis reaction of converting a reactive functional group such as an alkoxy group of vinyltriethoxysilane grafted onto the olefin resin into a hydroxyl group, thereby improving the adhesion strength to the backsheet composed of the upper and lower glass substrates or the fluororesin Can be improved. At the same time, the aminosilane compound is also involved as a reactant in the direct copolymerization reaction, thereby providing a moiety having an amine functional group in the aminosilane-modified olefin resin.

The aminosilane compound may be a compound represented by the following general formula (1).

[Chemical Formula 1]

SiR ¹ _m R ² _(4-m)

In the above formula (1), R ¹ represents - (CH ₂ ) _n NR ³ R ⁴ bonded to a silicon atom, R ³ and R ⁴ each independently represent hydrogen or R ⁵ NH ₂ bonded to a nitrogen atom , And R < ⁵ > represents an alkylene having 1 to 6 carbon atoms.

R ² is a halogen bonded to a silicon atom, an amine group -R ⁶ R ⁷ Or -R ⁷ , R ⁶ is an oxygen or sulfur atom, and R ⁷ is hydrogen, an alkyl group, an aryl group, an aralkyl group or an acyl group.

In this case, m is an integer of 1 to 4, and n is an integer of 0 or more.

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 may be an aryl group having 6 to 18 carbon atoms or 6 to 12 carbon atoms such as a phenyl group and the aralkyl group may be an aralkyl group having 6 to 48 carbon atoms or 6 to 30 carbon atoms such as a benzyl group have.

Preferably, in the above formula (1), R ² represents -R ⁶ R ⁷ bonded to a silicon atom, R ⁶ represents an oxygen atom, and R ⁷ represents hydrogen, an alkyl group, an aryl group, an aralkyl group or an acyl group And R ¹ represents - (CH ₂ ) _n NR ³ R ⁴ bonded to a silicon atom, and R ³ And R ⁴ may be hydrogen, or R ³ may represent hydrogen and R ⁴ may represent R ⁵ NH ₂ , wherein R ⁵ may be alkylene having 1 to 3 carbon atoms. In this case, n may be an integer of 2 to 5.

The aminosilane compound may be added in the step of modifying the olefin resin, for example, in the step of producing the aminosilane-modified olefin resin.

In addition, the aminosilane compound can stably maintain the overall properties of the composition as intended, without adversely affecting other components contained in the composition, for example, a UV stabilizer as described later.

The aminosilane compounds usable in the embodiments of the present application are silane compounds containing an amine group, and are not particularly limited as long as they are primary amines and secondary amines. For example, aminotrialkoxysilane, aminodialkoxysilane and the like can be used as the aminosilane compound, and examples thereof include 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane Aminopropyltriethoxysilane (APTES), bis [(3-triethoxysilyl) propyl] amine, bis [(3-trimethoxysilyl) propyl] amine, 3-aminopropylmethyldiethoxysilane, Dimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine (DAS), aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldimethylamine Aminoethylaminomethyltriethoxysilane, aminoethylaminomethylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropyltriethoxysilane, (N-phenylamino) methyltriethoxysilane, (N-phenylamino) methyltrimethoxysilane, (N-phenylamino) methyltrimethoxysilane, (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino) propylmethyldimethoxysilane, 3- (N-phenylamino) propylmethyldiethoxysilane and N- (N-butyl) -3-aminopropyltrimethoxysilane. More than species. The aminosilane compound may be used alone or in combination.

0.01 to 0.5 parts by weight, 0.1 to 0.25 parts by weight, 0.2 to 0.5 parts by weight, 0.5 to 1.25 parts by weight, 0.1 to 1.25 parts by weight, and 0.1 to 0.5 parts by weight, based on 100 parts by weight of the total solid content of the olefin resin composition. To 1.5 parts by weight or 0.2 to 2.0 parts by weight. In this weight ratio, the physical properties of the resin composition can be effectively controlled, the adhesive strength to the front substrate and the back sheet can be increased, and the activity of other additives contained in the resin composition can be kept excellent. If the content of the aminosilane compound to be added is excessive, discoloration of the resin may occur prematurely or a large amount of gel may be formed during the process, thereby adversely affecting the appearance of the sheet to be produced.

The aminosilane compound may be used in an amount of from 1 to 35 parts by weight, for example, from 2 to 6 parts by weight, from 2 to 5.5 parts by weight, from 5 to 5.5 parts by weight, from 2 to 5 parts by weight based on 100 parts by weight of vinyltriethoxysilane, 5 to 15 parts by weight, 5 to 15 parts by weight, 10 to 35 parts by weight, 5 to 35 parts by weight, 15 to 33.3 parts by weight or 2 to 33.3 parts by weight of the total amount of the olefin resin composition 1 to 40 parts by weight, for example, 2 to 30 parts by weight, 2 to 25 parts by weight, 1 to 25 parts by weight, 2 to 6 parts by weight, 1 to 10 parts by weight, 4 to 10 parts by weight, 12 to 12 parts by weight, 5 to 10 parts by weight, 2 to 10 parts by weight or 2 to 5 parts by weight. When the olefin resin composition adjusted to the content of the aminosilane compound is reactively extruded, the adhesiveness between the encapsulant for the optoelectronic device and the front substrate is excellent, and when the aminosilane compound is contained in excess, The Yellowness Index of the ash is increased, which may affect other properties of the sealing material.

The aminosilane compound and the vinyltriethoxysilane are similar in terms of the silyl group but are different in that they each contain an amine functional group and have an unsaturated group. The olefin resin composition may include both of the two substances, , It is possible to provide excellent adhesion performance as compared with the case where only one of the two materials is contained. Here, the addition of the aminosilane compound may absolutely improve the adhesion performance irrespective of the content of vinyltriethoxysilane. However, even when vinyltriethoxysilane having the same content is used, , The adhesion performance can be further improved.

Further, according to the embodiments of the present application, it is possible to provide an encapsulant having an adhesive property remarkably superior to that in the case where an encapsulant is simply produced using an alkylsilane or an alkylamine. For example, in the case of using only alkylamine, unlike vinylsilane or aminosilane compound, the alkylamine does not participate in the grafting polymerization reaction and remains as a material remaining in the system, and then moves to the surface of the modified olefin resin Or moved to the surface of the sheet during production with a sheet-like encapsulant. Therefore, the long term durability is deteriorated due to the materials remaining in the system. Further, in the case of some alkyl amines, there is also a problem that the melting point is about 27 to 29 캜 and the miscibility with other reactants, for example, a liquid silane compound is poor at a temperature range lower than the melting point.

In one example, the olefin resin composition comprises a radical initiator. The radical initiator may serve to initiate a reaction in which vinyltriethoxysilane grafts to the olefin resin.

The radical initiator is not particularly limited as long as it can initiate the radical polymerization of the vinyl group, and examples thereof include one or more selected from the group consisting of organic peroxides, hydroperoxides and azo compounds. Specific examples thereof include t-butylperoxyperoxide, di-t-butylperoxide, di-cumylperoxide, 2,5-dimethyl-2,5-di (t- butylperoxy) Dialkyl peroxides such as 2,5-di (t-butylperoxy) -3-hexyne; Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane, and t-butyl hydroperoxide; Diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; butyl peroxy isobutyrate, t-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t- Butyl peroxybenzoate, di-t-butylperoxy phthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl- (Benzoyl peroxy) -3-hexyne; And ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, azo compounds such as lauryl peroxide, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) , But the present invention is not limited thereto.

The radical initiator may be included in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the solid content in the total olefin resin composition.

The olefin resin composition according to the embodiments of the present application may further include at least one additive selected from a light stabilizer, a UV absorber, and a heat stabilizer, if necessary.

The light stabilizer may act to prevent photo-oxidation by capturing the active species of the initiation of photo-initiation of the olefin resin according to the application to which the composition is applied. The type of light stabilizer that can be used is not particularly limited, and for example, a known compound such as a hindered amine compound or a hindered piperidine compound can be used.

The UV absorber can act to absorb ultraviolet rays from sunlight or the like and convert it into harmless thermal energy in the molecule to prevent excitation of the active species of photo-initiation initiation in the olefin resin, depending on the use of the composition . The specific kind of the UV absorber that can be used is not particularly limited and includes, for example, inorganic UV such as benzophenone, benzotriazole, acrylonitrile, metal complex salt, hindered amine, ultrafine titanium oxide, Absorbing agent and the like, or a mixture of two or more thereof.

Examples of the heat stabilizer 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 diphosphite Of thermal stabilizers; And a reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, and one or more of the above- have.

In the olefin resin composition, the content of the light stabilizer, the UV absorber and / or the heat stabilizer is not particularly limited. That is, the content of the additive can be appropriately selected in consideration of the use of the resin composition, the shape and the density of the additive, and is suitably adjusted within the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the total solid content of the resin composition Lt; / RTI >

In addition to the above-described components, the exemplary olefin resin composition may further suitably include various additives known in the art depending on the application to which the resin component is applied.

In another embodiment of the present application, a modified olefin resin such as a silane-modified olefin resin or an aminosilane-modified olefin resin can be provided by using the olefin resin composition. The modified olefin resin may be, for example, May be included in the encapsulant for the device. The modified olefin resin can be used as an encapsulant for encapsulating an element in various optoelectronic devices. However, the modified olefin resin can be used as an industrial material applied to, for example, a temperature-elevated lamination process.

In one example, the encapsulant for optoelectronic devices comprises a modified olefinic resin, such as a silane modified olefinic resin or an aminosilane-modified olefinic resin, prepared by grafting an olefinic resin composition according to the present application. The silane-modified olefin resin may be formed by grafting the vinyltriethoxysilane to a main chain containing a polymerization unit of an olefin-based monomer. The aminosilane-modified resin is formed by grafting the vinyltriethoxysilane and the aminosilane compound on a main chain containing a polymerization unit of an olefin-based monomer, and the moiety of which the hydrocarbon group of some silyl group is converted into a hydroxy group (A ) And a moiety (B) into which a terminal amine functional group is introduced. The silane-modified moiety (A) with the amine group and the silane-modified moiety (B) may have a ratio of 99: 1 to 40:60.

As described above, the encapsulating material of the present application can have excellent long-term preservability by including a copolymer formed by grafting vinyltriethoxysilane onto an olefin resin, and in one example, the encapsulating material is represented by the following general formula 1 . The encapsulant of the present application maintains the melt index value at the time when the initial encapsulant is manufactured even after a considerable time has elapsed, and accordingly, a functional group showing adhesiveness in the encapsulant such as methoxysilyl derived from an unsaturated silane compound Alkoxysilyl groups such as vinyl groups or ethoxysilyl groups can not be spontaneously reacted during storage and thus can be stored without losing adhesion for a longer period of time.

[Formula 1]

MI _a - MI _b ? 0.9 g / 10 min

In the general formula (1), MIa represents the melt index of the encapsulant measured within 24 hours from the time when the encapsulant was manufactured, and MI _b represents the melt index of the encapsulant at room temperature and humidity Of the encapsulant measured after storage for 28 days or more, for example, 28 to 84 days, 28 to 56 days, or 56 days to 84 days from the time point. In one embodiment, the MI _b is the melting temperature of the encapsulant measured after storing the encapsulant in a polyethylene encapsulation bag for 28 days, 56 days or 84 days from the time when the encapsulant was prepared at room temperature and humidity conditions, And preferably represents the melt index of the encapsulant measured after storage for 84 days.

The melt index represents the amount (g / 10 min) of the resin extruded for 10 minutes under a load of 2.16 Kg at a temperature of 190 캜. The larger the value of the melt index, the more the resin flow It means excellent. As used herein, the normal temperature means a temperature in the natural state without being warmed or warmed, and may be, for example, 20 to 30 ° C or 23 to 25 ° C. In addition, the above-mentioned humidity-conditioning condition means a condition that a constant humidity, for example, a relative humidity is kept constant under a condition of 5 to 50%, for example, 10 to 30% The ash can be measured from the time when it is manufactured. At this time, one day can be calculated based on exactly 24 hours.

The sealing material of the present application satisfies the above general formula (1) by including the reaction extrudate of the olefin resin composition containing vinyltriethoxysilane. Thus, in the present application, the sealing material is stored for a considerable time, for example, For example, even after four weeks, eight weeks, or twelve weeks have elapsed, it is possible to provide an encapsulant having a significantly reduced amount or a decreasing rate of the melt index value.

In one example, the range of MI _a - MI _b is 0.9 g / 10 min or less, for example, 0.8 g / 10 min or less, 0.7 g / 10 min or less, 0.6 g / 10 min or less, 0.5 g / g / 10 min or less, preferably 0.3 g / 10 min or less, and the melt index value may not decrease even after a considerable time, so the lower limit value is not particularly limited. For example, the range of MI _a - MI _b may include a value of 0 or less.

As described above, the encapsulant of the present application retains the melt index value at the time when the initial encapsulant is manufactured even after a considerable time has elapsed, and accordingly, a functional group showing adhesiveness in the encapsulant, for example, an unsaturated silane compound The resulting alkoxysilyl group such as a methoxysilyl group or an ethoxysilyl group does not spontaneously react during storage and can be stored without losing adhesion for a longer period of time. For example, the value of MI _b may be 2.0 g / 10 min or more, for example, 2.1 g / 10 min or more, 2.2 g / 10 min or 2.3 g / 10 min or more Or more, but is not limited thereto.

In one example, when the encapsulant according to the present application comprises the aminosilane-modified olefin resin, even when laminated at a low lamination temperature, it can have excellent adhesion to a front substrate, for example, a glass substrate.

For example, the encapsulant containing the aminosilane-modified olefin resin may be peeled off at a temperature of 110 DEG C, for example, 110 DEG C, 130 DEG C, 140 DEG C, 150 DEG C or 160 DEG C, 15 mm or more, 70 N / 15 mm or more, 80 N / 15 mm or more, a peeling force of the sealing material for the optoelectronic device on the glass substrate measured at an angle and a peeling speed of 50 mm / More than 90 N / 15 mm, more than 100 N / 15 mm, more than 110 N / 15 mm, more than 60 N / 15 mm, more than 120 N / 15 mm, more than 130 N / 15 mm, more than 140 N / / 15 mm or more, 165 N / 15 mm or more, 170 N / 15 mm or more, 180 N / 15 mm or more, or 200 N / 15 mm or more.

Further, the encapsulant of the present application has excellent light transmittance. For example, the encapsulant may have a total light transmittance of at least 90.0%, such as at least 91.0%, at least 91.2%, at least 91.3%, at least 91.5%, at least 91.7%, at least 91.9% Can be adjusted to have the total light transmittance in the above-mentioned range, taking into consideration the photoelectric efficiency of the device.

Further, the encapsulating material also has a low haze value and exhibits excellent transparency. For example, the encapsulant may have a haze of less than 4.0%, for example, less than 3.5%, less than 3.0%, less than 2.5%, less than 2.0%, or less than 1.5%, in consideration of the photoelectric efficiency of the optoelectronic device. Value. &Lt; / RTI >

The total light transmittance and haze are values measured with a haze meter for light having a wavelength of 200 nm or more, for example, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm And may be a value measured with a haze meter, preferably for light at a wavelength of 550 nm. Also, for example, the total light transmittance and haze may be measured values after lamination to a glass substrate at a temperature of 110 캜, 130 캜 or 150 캜, but are not limited thereto.

Also, the total light transmittance can be measured using UV / Vis spectroscopy. In this case, the total light transmittance is a value measured using UV / Vis spectroscopy for light having a wavelength of 200 nm or more, for example, light having a wavelength of 200 to 1300 nm, 250 to 1300 nm, or 300 to 1100 nm .

The encapsulant for the optoelectronic device may include a non-modified olefin resin other than the modified olefin resin. The specific type of non-modified olefin resin that can be used is not particularly limited. For example, as the non-modified olefin resin, polyethylene may be used. Specifically, an ethylene /? - olefin copolymer belonging to the same category as the ethylene /? - olefin copolymer used in the production of the modified olefin resin Can be used.

The weight ratio of the non-modified olefin resin to the modified olefin resin may be from 1: 1 to 20: 1, such as from 1: 1 to 10: 1, from 1: 1 to 5: 1, or from 2: . If the amount of the unmodified olefin resin is too large, the adhesion performance expressed by the modified olefin resin tends to deteriorate. If the amount of the unmodified resin is too small, the adhesion performance expressed by the modified olefin resin develops early, So that the sheet formability may be undesirable.

The content of the non-modified olefin resin is not particularly limited and may be selected in consideration of desired physical properties. For example, the non-modified olefin resin may be contained in an amount of 0.01 to 3,000 parts by weight, 100 to 2000 parts by weight, or 90 to 1000 parts by weight based on 100 parts by weight of the modified olefin resin .

The encapsulation material may be contained in a state in which the respective components are uniformly mixed in the state, or may be contained in a state of being molded by various molding methods such as hot melt extrusion and T-die molding.

The shape of the sealing member is not particularly limited, and may be, for example, a sheet or a film. In this case, the thickness of the encapsulating material can be adjusted to about 10 탆 to 2,000 탆, or about 100 탆 to 1250 탆, in consideration of the supporting efficiency and breakage possibility of the element, the weight reduction of the apparatus, and workability. However, the thickness of the encapsulant may vary depending on the specific application to which it is applied.

Another embodiment of the present application provides a method of manufacturing an encapsulant for an optoelectronic device using the above-described olefin resin composition. In one example, the method for producing the encapsulant for optoelectronic devices comprises the step of producing the above-described modified olefin resin.

The method for producing the modified olefin resin is not particularly limited. For example, the olefin resin composition containing the olefin resin and the unsaturated silane compound is added to the reactor, mixed in the reactor, and heated and melted in the presence of an appropriate radical initiator Or an olefin resin composition comprising an olefin resin, an unsaturated silane compound and an aminosilane compound is added to the reactor, mixed in the reactor, and then heated and melted in the presence of a suitable radical initiator Rafting extrusion reaction.

The type of the reactor in which the modified 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 an extruder or an extruder with a hopper. When such a reactor is used, the modified olefin resin may be obtained by, for example, extruding a liquid unsaturated silane compound, an aminosilane compound and a radical initiator into an olefin resin heated and melted through an extruder, A radical initiator, an aminosilane compound, and an unsaturated silane compound, followed by heating and melting in an extruder for reaction.

Other additives such as an ultraviolet absorber, a heat stabilizer or a UV stabilizer may be added to the modified olefin resin prepared as described above, and the additives may be added into the reactor before or after the modified olefin resin is formed. For example, the process may be simplified by simultaneously producing the modified olefin resin and mixing with additives in one reactor.

Other additives may be introduced into the reactor as they are, or they may be mixed in the form of a master batch and mixed. The master batch means a pellet-shaped raw material in which additives to be added are concentrated and dispersed at a high concentration. In general, when a plastic raw material is processed by a method such as extrusion or injection, Is used to introduce additives.

The method for introducing the additive into the reactor in which the modified 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 or a method of mixing with an olefin resin or the like in a hopper and inputting the mixture may be used.

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, the conditions such as the temperature and the time, and the production method of the master batch are not particularly limited and may be suitably selected in consideration of raw materials to be used have.

In embodiments of the present application, an encapsulant for an optoelectronic device can be produced by molding the olefin resin composition according to the present application into a film or sheet form. Such a molding method is not particularly limited, and it is possible to produce an encapsulating material by sheeting or filming by a conventional process such as a T-die process or extrusion. In embodiments of the present application, the production of the modified olefin resin using the above-mentioned olefin resin composition and the in-situ process can be carried out using a device in which the filming or sheeting process is connected to each other.

According to another embodiment of the present application, it is possible to provide an optoelectronic device including an optoelectronic device encapsulated by an encapsulant made from the above-mentioned olefin resin composition.

The optoelectronic component that is encapsulated may be a light emitting or light sensing part, such as a photovoltaic cell, a light emitting diode or an organic light emitting diode, for example.

The method for encapsulating the optoelectronic device using the olefin resin composition according to the specific structure of the optoelectronic device or the embodiments of the present application is not particularly limited and may be applied according to the purpose of the device.

For example, when the optoelectronic device is a photovoltaic device, the optoelectronic device may include a front substrate 11, 21, a backsheet 12, 22, and a front substrate 11, 21, And the photovoltaic elements 13 and 23 encapsulated by the sealing materials 14 (a), 14 (b), and 24 between the backsheets 12 and 22, The encapsulant may be made from an olefin resin composition according to embodiments of the present application.

Such a solar cell module is manufactured by a usual molding method such as a lamination method in which a front substrate, an encapsulant, a photovoltaic element, a backsheet, etc. are laminated in accordance with a desired structure and then heated and pressed while being vacuum- can do. In this case, the processing conditions of the lamination method are not particularly limited and can be generally carried out at a temperature of 90 to 230 캜, or 110 to 200 캜 for 1 to 30 minutes, or 1 to 10 minutes.

The specific types of the front substrate, the back sheet, and the photovoltaic device that can be used in the above are not particularly limited. For example, the front 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, And a surface layer containing a polymer. For example, it may be a multilayer film in which a fluoropolymer layer is formed on both sides of a polyethylene terephthalate (PET) film. The photovoltaic device may be, for example, a silicon wafer type active layer or a thin film active layer formed by chemical vapor deposition (CVD) or the like.

Embodiments of the present application can provide an encapsulant having excellent long-term storage properties and excellent adhesion with the front substrate and backsheet included in various optoelectronic devices. Further, it is possible to provide an encapsulant which can excellently maintain the workability and economical efficiency of the device manufacturing without adversely affecting components such as optoelectronic devices or wiring electrodes encapsulated in the optoelectronic device and the working environment.

1 and 2 are cross-sectional views exemplarily showing a solar cell module which is an optoelectronic device according to one example of the present application.
Fig. 3 is a graph showing the melt indexes of the sealing materials of Examples and Comparative Examples of the present application. Fig.

Hereinafter, the present application will be described in detail by way of examples and comparative examples of the present application, but the scope of the present application is not limited by the following examples.

< Silane Modified ethylene /? - olefin copolymer and amino Silane Preparation of Modified Ethylene /? - olefin Copolymer>

Manufacturing example One

95.01 parts by weight of an ethylene /? - olefin copolymer having a density of 0.870 g / cm ³ and an MFR of 5 g / 10 min under a load of 2.16 kg at 190 占 폚, 4.89 parts by weight of vinyltriethoxysilane (VTES) , And 0.1 part by weight of 5-bis (tert-butylperoxy) -2,5-dimethylhexane (Luperox ^® 101) were melt kneaded at 220 ° C. (Heated to melt and agitate) by grafting at 180 rpm, to prepare a master batch of the silane-modified ethylene /? - olefin copolymer. (Based on 100 parts by weight of the total, each part by weight represents wt%).

Manufacturing example 2

95.01 parts by weight of an ethylene /? - olefin copolymer having a density of 0.870 g / cm ³ and an MFR of 5 g / 10 minutes under a load of 2.16 kg at 190 占 폚, 4.40 parts by weight of vinyltriethoxysilane (VTES) 0.49 part by weight of 3-aminopropyltrimethoxysilane (APTMS) and 2.5 parts by weight of 2,5-bis (tert-butylperoxy) -2-t-butylperoxy , 5-dimethylhexane, and Luperox ^® 101) were graft-extruded (heated and melt stirred) at 220 ° C. at 180 ° C. using a twin-screw extruder to prepare a masterbatch of the aminosilane-modified ethylene / α-olefin copolymer Respectively. (Based on 100 parts by weight of the total, each part by weight represents wt%).

compare Manufacturing example One

Except that 4.89 parts by weight of vinyltrimethoxysilane was used instead of 4.89 parts by weight of vinyltriethoxysilane used in Production Example 1 to prepare a master batch of silane-modified ethylene /? - olefin copolymer Respectively.

compare Manufacturing example 2

Except that 4.40 parts by weight of vinyltrimethoxysilane was used instead of 4.40 parts by weight of vinyltriethoxysilane used in Production Example 2 to prepare a master batch of aminosilane-modified ethylene /? - olefin copolymer .

compare Manufacturing example 3

Except that a mixture (VTES: VTMS = 1: 1) of 2.445 parts by weight of vinyltriethoxysilane and 2.445 parts by weight of vinyltrimethoxysilane was used instead of 4.89 parts by weight of vinyltriethoxysilane used in Production Example 1 1 to prepare a master batch of the silane-modified ethylene /? - olefin copolymer.

compare Manufacturing example 4

Except that a mixture (VTES: VTMS = 1: 1) of 2.20 parts by weight of vinyltriethoxysilane and 2.20 parts by weight of vinyltrimethoxysilane was used instead of 4.40 parts by weight of vinyltriethoxysilane used in Production Example 2 2, a master batch of an aminosilane-modified ethylene /? - olefin copolymer was prepared.

compare Manufacturing example 5

Except that a mixture (VTES: VTMS = 3: 7) of 1.32 parts by weight of vinyltriethoxysilane and 3.08 parts by weight of vinyltrimethoxysilane was used instead of 4.40 parts by weight of vinyltriethoxysilane used in Production Example 2 2, a master batch of an aminosilane-modified ethylene /? - olefin copolymer was prepared.

The ingredients of each production example are summarized in Table 1 below.

Base resin
(Content, density)
Silane compound Luperox®101
(content)
Aminosilane
(content)
VTES content
(Based on total silane)
VTES
(content) VTMS
(content) Production Example 1 95.01 wt%
(d = 0.870) 4.89 wt% - 0.1 wt% - 100 wt% Production Example 2 95.01 wt%
(d = 0.870) 4.40 wt% - 0.1 wt% APTMS
0.49 wt% 90 wt% Comparative Preparation Example 1 95.01 wt%
(d = 0.870) - 4.89 wt% 0.1 wt% - - Comparative Production Example 2 95.01 wt%
(d = 0.870) - 4.40 wt% 0.1 wt% APTMS
0.49 wt% - Comparative Production Example 3 95.01 wt%
(d = 0.870) 2.445 wt% 2.445 wt% 0.1 wt% - 50 wt% Comparative Production Example 4 95.01 wt%
(d = 0.870) 2.20 wt% 2.20 wt% 0.1 wt% APTMS
0.49 wt% 45 wt% Comparative Preparation Example 5 95.01 wt%
(d = 0.870) 1.32 wt% 3.08 wt% 0.1 wt% APTMS
0.49 wt% 27 wt% VTES: vinyltriethoxysilane
VTMS: vinyltrimethoxysilane
APTMS: 3-aminopropyltrimethoxysilane

< Encapsulant And photovoltaic module &

Example 1 and 2

Α-olefin copolymer having a density of 0.870 g / cm ³ and MFR of 5 g / 10 min under a load of 190 ° C. and 2.16 kg, respectively, of the modified ethylene / α-olefin copolymer prepared in Production Examples 1 and 2, (Uvinul 5050H) 1000 ppm, UV absorber (TINUVIN UV531) 1000 ppm, and antioxidant 1 (Irganox 1010) 500 ppm in the final sheet were added to the resin in which 200 g and 400 g of olefin copolymer were respectively prepared and mixed at a ratio of 1: And 18 g of an additive master batch containing 500 ppm of antioxidant 2 (Irgafos 168) were added and mixed, and the mixture was introduced into a hopper of a film forming machine having a twin screw extruder (? 19 mm) and a T die (width: 200 mm) An extrusion temperature of 180 ° C and a take-off speed of 3 m / min to produce a sheet-like encapsulant having a thickness of about 500 μm.

(Thickness: about 3 mm), the above-prepared sealing material having a thickness of 500 mu m, the crystalline silicon wafer photovoltaic device, the sealing material having a thickness of 500 mu m and the backsheet (polyvinyl fluoride resin sheet having a thickness of 20 mu m, PVDF / PET / PVDF) laminated in this order and pressed in a vacuum laminator at 150 캜 for 15 minutes and 30 seconds to form a photovoltaic module Respectively.

Comparative Example 1 to 5

Except that the master batches of the modified ethylene /? - olefin copolymers prepared in Comparative Preparation Examples 1 to 5 were used instead of the master batches of the modified ethylene /? - olefin copolymers Thereby producing a sheet-like encapsulant and a photovoltaic module.

Base resin (content, density)
Modified master batch Additive master batch
(content)
content VTES
(wt%) VTMS
(wt%) Aminosilane
(wt%) VTES content
(Based on total silane) Example 1 400g
(d = 0.870) 200g 4.89 wt% - - 100 wt% 18g Example 2 400g
(d = 0.870) 200g 4.40 wt% - APTMS
0.49 wt% 90 wt% 18g Comparative Example 1 400g
(d = 0.870) 200g - 4.89 wt% - 18g Comparative Example 2 400g
(d = 0.870) 200g - 4.40 wt% APTMS
0.49 wt% 18g Comparative Example 3 400g
(d = 0.870) 200g 2.445 wt% 2.445 wt% - 50 wt% 18g Comparative Example 4 400g
(d = 0.870) 200g 2.20 wt% 2.20 wt% APTMS
0.49 wt% 45 wt% 18g Comparative Example 5 400g
(d = 0.870) 200g 1.32 wt% 1.32 wt% APTMS
0.49 wt% 27 wt% 18g

Experimental Example

1. Measurement of Melt Index

For the measurement of the melt index, four samples were prepared for each of the examples and comparative examples of the encapsulant prepared in Examples 1 and 2 and Comparative Examples 1 to 5, and three samples of them were respectively polyethylene (PE) bag, and then heat sealed. The melt index of the encapsulant was measured by the following method. The results are shown in Table 3 below. And FIG. 3, respectively.

&Lt; Measurement method of melt index >

One sample of four samples prepared for each of the Examples and Comparative Examples was measured for the amount of the sample which had been melted for 10 minutes at a temperature of 190 DEG C and a load of 2.16 kg within one hour from the time of preparation, (PE) bag and stored in a thermo-hygrostat. The three samples were taken out after 4 weeks, 8 weeks and 12 weeks, respectively, and melted for 10 minutes under a temperature of 190 ° C and a load of 2.16 kg And the amount of the extracted sample was measured.

Sheet MI
(g / 10 min @ 190 < 0 > C)
Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 only VTES only VTES with APTMS only VTMS only VTMS with APTMS VTES + VTMS (VTMS: VTES = 1: 1) VTES + VTMS (VTMS: VTES = 1: 1) with APTMS VTES + VTMS (VTMS: VTES = 7: 3) with APTMS Early 3.47 3.32 4.38 3.32 4.17 3.26 2.93 After 4 weeks 3.56 3.08 2.64 1.38 2.84 1.93 1.58 After 8 weeks 3.24 2.6 0.76 0.82 1.98 1.14 0.45 After 12 weeks 3.15 2.46 0.09 0.25 0.57 0.69 0.29

As shown in Table 3, in the case of Examples 1 and 2 using only vinyltriethoxysilane alone, the melt index values measured at 4 weeks, 8 weeks, and 12 weeks respectively corresponded to the melt index values Which is shown in Fig.

On the other hand, in Comparative Examples 1 and 2 using only vinyltrimethoxysilane alone or in Comparative Examples 3 to 5 using vinyltriethoxysilane and vinyltriethoxysilane at the same time, after 4 weeks, 8 weeks, and 12 weeks It can be confirmed that the measured melt index value is smaller than the initial melt index value.

2. Measurement of 90 degree peel strength

In order to measure the peel strength of the encapsulant prepared in Examples 1 and 2 and Comparative Examples 1 to 5, a specimen similar to the manufactured photovoltaic module was separately prepared. The test piece was made of a sheet glass (thickness: about 3 mm), the above-prepared sealing material having a thickness of 500 탆 and a backing sheet (a polyvinyl fluoride resin sheet having a thickness of 20 탆, polyethylene terephthalate having a thickness of 250 탆 and polyvinyl fluoride Laminated sheet of resin sheet: PVDF / PET / PVDF) were laminated in this order and laminated in a vacuum laminator at 150 캜 for 15 minutes and 30 seconds. After one day from the point of time when the test piece was prepared, the lower glass plate of the prepared test piece was fixed, and then the sealing material adhered to the backsheet was formed into a 15 mm wide rectangle and 50 mm / min in accordance with ASTM D1897 And the peel strength measured while being peeled off at a peel angle of 90 degrees are shown in Table 4 below.

Base resin (content, density)
Modified master batch 90 degree peel strength
(N / 15 mm)
content VTES
(wt%) VTMS
(wt%) Aminosilane
(wt%) VTES content
(Based on total silane) Example 1 400g
(d = 0.870) 200g 4.89 wt% - - 100 wt% 85.0 Example 2 400g
(d = 0.870) 200g 4.40 wt% - APTMS
0.49 wt% 90 wt% 250 Comparative Example 1 400g
(d = 0.870) 200g - 4.89 wt% - 80.0 Comparative Example 2 400g
(d = 0.870) 200g - 4.40 wt% APTMS
0.49 wt% 265 Comparative Example 3 400g
(d = 0.870) 200g 2.445 wt% 2.445 wt% - 50 wt% 75.0 Comparative Example 4 400g
(d = 0.870) 200g 2.20 wt% 2.20 wt% APTMS
0.49 wt% 45 wt% 255 Comparative Example 5 400g
(d = 0.870) 200g 1.32 wt% 1.32 wt% APTMS
0.49 wt% 27 wt% 260

As shown in Table 4, when aminosilane is used simultaneously with vinyltriethoxysilane, it exhibits excellent adhesive strength even under various lamination temperature and time conditions, and even when laminated at a low lamination temperature of 110 DEG C It can be confirmed that it has an adhesive strength.

1, 2: Solar cell module
11, 21: front substrate
12, 22: back sheet
13, 23: photovoltaic device
14 (a), 14 (b), 24: Encapsulation material

Claims

An olefin resin composition comprising an olefin resin, an unsaturated silane compound, and a radical initiator, wherein the unsaturated silane compound comprises vinyltriethoxysilane.

The olefin resin composition according to claim 1, wherein the vinyltriethoxysilane is contained in an amount of 0.1 to 10.0 parts by weight based on 100 parts by weight of solid content in the total olefin resin composition.

The olefin resin composition according to claim 1, further comprising an aminosilane compound.

4. The olefin resin composition according to claim 3, wherein the aminosilane compound is a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
SiR ¹ _m R ² _(4-m)
In Formula 1,
R ¹ represents - (CH ₂ ) _n NR ³ R ⁴ bonded to a silicon atom,
R ³ and R ⁴ each independently represents hydrogen or R ⁵ NH ₂ bonded to a nitrogen atom,
R ⁵ represents alkylene,
R ² is a halogen bonded to a silicon atom, an amine group -R ⁶ R ⁷ Or -R ⁷ ,
R < ⁶ > is an oxygen or sulfur atom,
R ⁷ represents hydrogen, an alkyl group, an aryl group, an aralkyl group or an acyl group,
m is an integer of 1 to 4, and n is an integer of 0 or more.

4. The olefin resin composition according to claim 3, wherein the aminosilane compound is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the silane compound in the total olefin resin composition.

The olefin resin composition according to claim 1, wherein the olefin resin comprises an ethylene /? - olefin copolymer.

The olefin resin composition according to claim 6, wherein the density of the ethylene /? - olefin copolymer is 0.85 g / cm ³ to 0.96 g / cm ³ .

The olefin resin composition according to claim 6, wherein the MFR of the ethylene /? - olefin copolymer is 1.0 g / 10 min to 50.0 g / 10 min at 190 ° C under a load of 2.16 kg.

The olefin resin composition according to claim 1, wherein the radical initiator is at least one member selected from the group consisting of an organic peroxide, a hydroperoxide, and an azo compound.

The olefin resin composition according to claim 1, wherein the radical initiator is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the solid content in the total olefin resin composition.

The olefin resin composition according to claim 1, further comprising at least one additive selected from the group consisting of a light stabilizer, a UV absorber, and a heat stabilizer.

An encapsulant for an optoelectronic device comprising a modified olefin resin which is a reaction extrudate of the olefin resin composition of claim 1.

The encapsulating material for an optoelectronic device according to claim 12, which satisfies the following general formula (1)
[Formula 1]
MI _a - MI _b ? 0.9 g / 10 min
In the general formula (1), MI _a represents the melt index of the encapsulant measured within 24 hours from the time when the encapsulant was manufactured, MI _b represents the melt index of the encapsulant at room temperature and humidity Of the encapsulant measured after storage for more than 28 days from the point of time when the encapsulant was stored.

13. The encapsulant for optoelectronic devices of claim 12, further comprising a non-modified olefin resin.

15. The encapsulant of claim 14, wherein the non-modified olefin resin comprises an ethylene / alpha-olefin copolymer.

15. The encapsulant for optoelectronic devices according to claim 14, wherein the weight ratio of the non-modified olefin resin to the modified olefin resin is from 1: 1 to 20: 1.

An optoelectronic device comprising a front substrate, an encapsulant for an optoelectronic device according to claim 12, an optoelectronic device, and a backsheet.

A process for producing an encapsulating material for an optoelectronic device, comprising the step of extruding the olefin resin composition of claim 1 to produce a modified olefin resin.

19. The method according to claim 18, further comprising the step of adding a non-modified olefin resin to the modified olefin resin and shaping the modified olefin resin into a film or sheet shape.

20. The method of claim 19, wherein the step of producing the modified olefin resin and the step of shaping into a film or sheet form are performed in an in-situ process.