KR20150035075A - Olefin resin composition - Google Patents
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- KR20150035075A KR20150035075A KR20130115212A KR20130115212A KR20150035075A KR 20150035075 A KR20150035075 A KR 20150035075A KR 20130115212 A KR20130115212 A KR 20130115212A KR 20130115212 A KR20130115212 A KR 20130115212A KR 20150035075 A KR20150035075 A KR 20150035075A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
Abstract
Description
The present invention relates to an olefin resin composition, a process for producing an encapsulant for an optoelectronic device, an encapsulant film for an optoelectronic device produced by the composition, an optoelectronic device, and a process for producing 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.
Accordingly, there is a continuing need for an encapsulant for an optoelectronic device having excellent heat resistance durability in order to minimize deformation due to heat even when the long-term adhesive property is improved and even if exposed for a long time in a high temperature environment.
Embodiments of the present application provide olefin resin compositions, methods of making encapsulants for optoelectronic devices, encapsulant films for optoelectronic devices, and methods of making the optoelectronic devices.
One embodiment of the present application provides an olefin resin composition.
As used herein, the term " silane-modified olefin resin " and " silane-modified ethylene / alpha -olefin copolymer " refer to a copolymer comprising an unsaturated silane compound moiety in which the hydrocarbon group of the silyl group of the grafted olefin resin is converted to a hydroxyl group it means.
The olefin resin composition according to one embodiment of the present application includes an olefin resin, an unsaturated silane compound containing a vinyl group, a crosslinking agent, and a crosslinking assistant.
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 invention, an olefin resin grafted with an unsaturated silane compound can use a low density ethylene /? - olefin copolymer having many side chains, thereby improving the grafting efficiency and improving the adhesion of the sealing material .
Accordingly, embodiments of the present application specifically use an ethylene / alpha -olefin copolymer having a density of from about 0.85 g / cm 3 to 0.96 g / cm 3 or from about 0.85 g / cm 3 to 0.92 g / cm 3 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.
The unsaturated silane compound contained in the olefin resin composition is an unsaturated silane compound represented by the following formula (1). The unsaturated silane compound is grafted to the main chain containing the polymerization unit of the olefin-based monomer in the presence of a radical initiator, A modified olefin resin can be produced. That is, in the method for producing a copolymer of the present application, a graft polymer in which an unsaturated silane compound represented by the following formula (1) is grafted to an olefin resin can be prepared.
[Chemical Formula 1]
DSiR 1 p R 2 (3-p)
In the general formula (1), D represents an alkenyl bonded to a silicon atom. The alkenyl means a functional group having at least one unsaturated group such as a double bond, and the number of carbon atoms of the alkenyl may be 2 to 20, 2 to 12, or 2 to 6. The alkenyl may be, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl or gamma-methacryloxypropyl, and the like.
R 1 represents a hydroxyl group, halogen, an amine group or -R 3 R 4 bonded to a silicon atom, R 3 represents an oxygen or sulfur atom, R 4 represents an alkyl group, an aryl group or an acyl group, R 2 represents a silicon atom An alkyl group, an aryl group or an aralkyl group,
In one example, the R 1 may be a reactive functional group that can be hydrolyzed by the approach of the water present in the system, the R 1 are, for example, an alkoxy group, an alkylthio group, an aryloxy group, an acyloxy A halogen group, or an amine group. In this case, 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 and 1 to 4 carbon atoms, and examples of the acyloxy group include acyloxy groups having 1 to 12 carbon atoms And examples of the alkylthio groups include alkylthio groups having 1 to 12 carbon atoms.
In one embodiment, R 1 in the formula (1) is be an alkoxy, specifically, may be an alkoxy date of 1 to 12 carbon atoms, or 1 to 8 carbon atoms, in other embodiments from 1 to 4 carbon atoms An alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a butoxy group, and for example, a methoxy group or an ethoxy group may be used in some embodiments.
In addition, R 2 may be a non-reactive functional group. For example, R 2 may be hydrogen, an alkyl group, an aryl group, or an aralkyl group. 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 7 to 19 carbon atoms or 7 to 13 carbon atoms such as a benzyl group have
In Formula 1, p is an integer of 1 to 3, and may be 3 in some embodiments.
A specific example of the unsaturated silane compound of Formula 1 may be vinylalkoxysilane. For example, the unsaturated silane compound may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentoxysilane, vinyltriphenoxy Silane, vinyltriacetoxysilane, and the like. Among them, vinyltrimethoxysilane or vinyltriethoxysilane can be used, but the present invention is not limited thereto.
In one example, the olefin resin composition may include 0.1 to 10.0 parts by weight or 0.5 to 5.0 parts by weight of the unsaturated silane compound of Formula 1 based on 100 parts by weight of the solid content of the total olefin resin composition. Within this range, the adhesiveness of the copolymer, for example, adhesion to a glass substrate, a backsheet, and the like can be kept excellent.
Unless otherwise specified, unit weight parts in the present specification means weight ratios.
Further, according to embodiments of the present application, superior adhesion performance can be provided compared to the case of using an alkylsilane or an alkylamine alone. For example, in the case of using alkylamine alone, the alkylamine does not participate in the graft polymerization reaction, unlike vinylsilane, and remains as a material remaining in the system. The alkylamine then moves to the surface of the modified olefin resin, And is moved to the surface of the sheet as an 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 ° C and the miscibility with other reactants, for example, a liquid silane compound is poor.
In one example, the olefin resin composition includes a crosslinking agent and a crosslinking aid.
The crosslinking agent can serve as a radical initiator in the production of the silane-modified olefin resin, which will be described later, during the production of the sealing material, and can initiate the reaction of grafting the unsaturated silane compound to the olefin resin. In order to improve the heat durability of the encapsulating material to be described later by forming a crosslinking between the silane-modified olefin resin or between the silane-modified olefin resin and a non-modified olefin resin to be described later in the step of lamination to the olefin resin composition .
If the crosslinking agent is a crosslinkable compound capable of initiating the radical polymerization of the vinyl group or capable of forming the crosslinking described above, various crosslinking agents known in the art can be used in various ways. Examples thereof include organic peroxides, Hydroperoxides, and azo compounds may be used alone or in combination of two or more.
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.
Said organic peroxide may be an organic peroxide having a half-life temperature of 120 DEG C to 135 DEG C, for example 120 DEG C to 130 DEG C, 120 DEG C to 125 DEG C, preferably 121 DEG C for 1 hour. The "one-hour half-life temperature" in the above refers to the temperature at which the half life of the cross-linking agent becomes one hour. When the organic peroxide having a half-life temperature of 1 hour in the above-mentioned range is used as a crosslinking agent, the lamination for producing a later-described optoelectronic device Radical initiation reaction, i.e., cross-linking reaction, can proceed effectively at the process temperature.
The crosslinking agent is contained in an amount of 0.01 to 1 part by weight, for example, 0.05 to 0.55, 0.1 to 0.5, or 0.15 to 0.45 part by weight based on 100 parts by weight of the olefin resin composition. When the crosslinking agent is contained in an amount of less than 0.01 part by weight , The effect of improving the heat resistance is insignificant. If it exceeds 1 part by weight, the moldability of the encapsulating material sheet is reduced, which may cause a problem in the process, which may affect the physical properties of the encapsulating material.
Further, the olefin resin composition of the present application may contain a crosslinking aid in addition to the crosslinking agent. By including the crosslinking aid in the olefin resin composition, the degree of crosslinking between the olefin resin by the crosslinking agent described above can be increased, thereby further improving the heat durability of the sealing material described later.
The crosslinking aid is contained in an amount of 0.01 to 0.5 parts by weight, for example, 0.01 to 0.3, 0.015 to 0.2, or 0.016 to 0.16 parts by weight based on 100 parts by weight of the olefin resin composition, and the crosslinking aid is less than 0.01 part by weight The effect of improving the heat resistance is insignificant, and if it is contained in an amount exceeding 0.5 parts by weight, there arises a problem that affects the properties of the sealing material and the production cost may increase
As the crosslinking auxiliary, various crosslinking auxiliary agents known in the art may be used in the present application. For example, as the crosslinking auxiliary agent, a compound containing at least one unsaturated group such as an allyl group or a (meth) acryloxy group may be used .
Examples of the allyl group-containing compound include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diaryl phthalate, diallyl fumarate or diallyl maleate, Examples of the compound containing a (meth) acryloxy group include, for example, a poly (meth) acryloxy compound such as ethylene glycol diacrylate, ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate, But is not limited thereto.
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.
Another embodiment of the present application provides a method of producing an encapsulant for an optoelectronic device using the above-mentioned olefin resin composition. In one example, the method for producing the encapsulant for optoelectronic devices may comprise the steps of producing a silane-modified olefin resin and shaping it into a film or sheet form.
The method for producing the silane-modified olefin resin is not particularly limited. For example, an olefin resin composition containing an olefin resin and an unsaturated silane compound is added to a reactor, mixed in a reactor, and heated and melted in the presence of an appropriate radical initiator By grafting.
The radical initiator may serve to initiate a reaction in which the unsaturated silane compound is grafted to the olefin resin. The radical initiator is not particularly limited as long as it can initiate the radical polymerization of the vinyl group. For example, An organic peroxide, a hydroperoxide, and an azo compound.
The one-hour half-life temperature of the radical initiator may be, for example, not lower than 140 ° C, for example, not lower than 150 ° C, not lower than 160 ° C, not lower than 200 ° C, For example, it may be 250 ° C or less.
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 entire olefin resin composition
The type of the reactor in which the silane-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 a cylinder with an extruder or a hopper. In the case of using such a reactor, for example, an olefin resin, a radical initiator and an unsaturated silane compound are mixed in a hopper, and the resulting mixture is melt-kneaded, for example, by extruding an unsaturated silane compound and a radical initiator, The silane-modified olefin resin may be produced by heating and melting in a cylinder after the addition and reacting.
Other additives such as an ultraviolet absorber, a heat stabilizer or a UV stabilizer may be added to the silane-modified olefin resin prepared as described above, and the additives may be added to the reactor before or after the silane-modified olefin resin is formed. For example, the process may be simplified by simultaneously producing the silane-modified olefin resin and mixing with the additive 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 silane-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, Or a method in which the mixture is mixed with an olefin resin or the like in a hopper and the like can 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 invention, the silane-modified olefin resin, the crosslinking agent, and the crosslinking aid may be mixed and extruded to form a film or a sheet, thereby producing an encapsulant for an optoelectronic device.
In this case, a non-modified olefin resin may be further added to form a film or a sheet.
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, the ethylene /? - olefin copolymer which belongs to the same category as the ethylene /? - olefin copolymer used in the production of the silane- Can be used.
The content ratio of the non-modified olefin resin and the silane modified olefin resin may be 1: 1 to 20: 1. If the amount of the non-modified olefin resin is too large, the adhesion performance expressed by the silane-modified olefin resin tends to deteriorate. If the amount of the unmodified resin is too small, the adhesion performance expressed by the silane modified olefin resin develops early, And 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 .
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 preparation of the above-described silane-modified olefin resin, the preparation of the olefin resin composition comprising it, and the filming or sheeting process are performed in situ using an apparatus connected to each other .
According to the present application, the above-mentioned olefin resin composition can be used to provide a copolymer to be described later, that is, a silane-modified olefin resin according to the above-described production method. The copolymer can be, for example, .
In one example, the copolymer comprises a main chain comprising polymerized units of olefinic monomers; And a branched chain bonded to the main chain and represented by the following formula (2).
(2)
-SiR 5 l R 6 (3- l)
R 5 and R 6 each independently represents a halogen, an amine group, a group bonded to a silicon atom, -R 7 R 8 or -R 8 , R 7 represents an oxygen or sulfur atom, and R 8 represents hydrogen, an alkyl group, , An aralkyl group or an acyl group, and l is an integer of 1 to 3.
The copolymer includes, for example, a branch represented by the formula (2) grafted onto a main chain containing polymerized units of an olefin-based monomer, wherein the branch is a moiety in which a hydrocarbon group of some silyl group is converted to a hydroxy group And the like. By including the moiety in which the copolymer is converted into a hydroxy group, for example, it can form a hydrogen bond with a backsheet made of a fluororesin on top of the sealing material in the optoelectronic device, thereby providing excellent bonding strength.
In one example, the number of carbon atoms of the alkyl group in Formula 2 may be from 1 to 20, from 1 to 12, from 1 to 8, or from 1 to 4, for example, a methyl group, an ethyl group, a propyl group or a butyl group. It is not.
In addition, the number of carbon atoms of the aryl group may be 6 to 20, 6 to 18, or 6 to 12, and may be, for example, a phenyl group or a naphthyl group, but is not limited thereto.
The aralkyl group means an alkyl group in which at least one hydrogen atom of the hydrocarbon group of the alkyl group is substituted by an aryl radical, and the carbon number of the aralkyl group may be 7 to 40, 7 to 19, or 7 to 13. The carbon number of the aralkyl group means the total number of carbon atoms contained in the alkyl group and the aryl radical.
The alkylene group may be a straight or branched alkylene group having 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, and may be, for example, an ethylene group or a propylene group.
Also, the acyl group is a functional group represented by RC = O, wherein R represents an alkyl group or an aryl group, including, but not limited to, formyl, acetyl, propionyl or benzoyl. The number of carbon atoms of the alkyl group and the aryl group contained in the acyl group is the same as described above,
In one example, R 5 and R 6 May be a reactive functional group that can be hydrolyzed by the approach of water present in the system, and the description thereof is omitted for the same reason as the above-described reactive functional group.
In addition, R 5 or R 6 may be a non-reactive functional group, and the same description as the above-mentioned non-reactive functional group is omitted.
In Formula 2, l is an integer of 1 to 3, and may be 3 in some embodiments.
In one example, preferably, in the above formula (2), R 5 and R 6 each independently represent a hydroxy group or -R 7 R 8 bonded to a silicon atom, R 7 represents oxygen, and R 8 represents an alkyl group .
More preferably, in the above formula (2), R 5 and R 6 may represent a hydroxy group.
The alkyl group and alkylene in the above are the same as described above.
Further, according to the above-described method for producing an optoelectronic device using the olefin composition of the present application, it is possible to provide an encapsulant for an optoelectronic device including the copolymer. The copolymer may be used as an encapsulant for encapsulating an element in various optoelectronic devices, but is not limited thereto. For example, the copolymer may be used as an industrial material applied to a heating lamination process or the like.
In one example, the encapsulant for the optoelectronic device includes a silane-modified olefin resin prepared by grafting an olefin resin composition according to the present application, that is, the above-mentioned copolymer. As described above, the copolymer is formed by grafting an unsaturated silane compound represented by the above formula (1) in a main chain containing a polymerized unit of an olefin-based monomer. By including the branch of the above formula (2) And a moiety (A) converted to a gigahydroxy group.
In addition, the encapsulant for optoelectronic devices may have cross-linking between the olefin resins due to the cross-linking agent, so that the encapsulant for optoelectronic devices can have improved heat durability.
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.
According to the present application, it is possible to provide an optoelectronic device including an optoelectronic device encapsulated by an encapsulant produced 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
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 process conditions of the lamination method are not particularly limited, and are usually carried out at a temperature of 90 to 230 DEG C, 110 to 200 DEG C or 110 to 160 DEG C for 1 to 30 minutes, or 1 to 10 minutes can do.
In the case of the olefin resin composition according to the embodiments of the present application, the reactive silyl group of the silane-modified moiety of the chemically unstable silane-modified olefin resin through the extrusion process, for example, a methoxysilyl group (Si-O-CH 3 ) is converted to a silanol group (Si-OH) in the modularization process such as lamination as described above, and forms a chemical covalent bond by dehydration condensation with residues such as a hydroxyl group on the front substrate surface of the optoelectronic device So that a high adhesive force can be exhibited.
In addition, fluorine and silanol groups form a hydrogen bond even at the interface with the backsheet having a surface layer containing a fluoropolymer which is frequently used in recent years, so that high interfacial adhesion can be exhibited unlike conventional sealing materials.
Further, in the case of the olefin resin composition according to the embodiments of the present application, the crosslinking reaction between the silane-modified olefin resin or between the silane-modified olefin resin and the non-modified olefin resin by the crosslinking agent and the crosslinking aid The sealing material sheet having excellent heat resistance and durability can be produced.
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.
In the embodiments of the present application, it is possible to provide an encapsulant having excellent adhesion with the front substrate and the backsheet included in various optoelectronic devices, in particular, with improved long-term adhesive property and heat resistance. 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.
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.
<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 minutes under a load of 2.16 kg at 190 占 폚, 4.89 parts by weight of vinyltrimethoxysilane (VTMS) 2,5-Bis (tert-butylperoxy) -2,5-dimethylhexane, Luperox ® 101) 0.1 part by weight Using a twin screw extruder, 220 parts by weight of 220 Deg.] C to prepare a master batch of the modified ethylene / alpha -olefin copolymer. (Based on 100 parts by weight of the total, each part by weight represents wt%).
< Encapsulant And photovoltaic module &
Example One
A master batch of the modified ethylene /? - olefin copolymer prepared in Preparation Example 1, an ethylene /? - olefin copolymer having a density of 0.865 g / cm 3 and an MFR of 5 g / 10 min under a load of 2.16 kg (1: 2), 0.54 parts by weight of a crosslinking agent t-butylperoxy 2-ethylhexyl carbonate (1 hour half-life temperature: 121 占 폚) , 0.16 part by weight of triallyl isocyanurate was further added and 1,000 ppm of a light stabilizer (Uvinul 5050H), 1000 ppm of a UV absorber (TINUVIN UV 531), 500 ppm of an antioxidant 1 (Irganox 1010) 2.9 parts by weight 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 single screw extruder (? 19 mm) and a T die (width: 200 mm) , Extrusion temperature 100 DEG C, 50 rpm To produce a sheet-like encapsulant having a thickness of about 500 탆.
(Thickness: about 8 mm), the sealing material having a thickness of 500 mu m prepared above, 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 38 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.
Example 2 and 7
Except that the content of the base resin, the additive master batch, the crosslinking agent t-butylperoxy 2-ethylhexylcarbonate and the crosslinking aid triallyl isocyanurate used in Example 1 was changed as shown in Table 1 1, a sheet-like encapsulant and a photovoltaic module were produced.
Example 8
(T-butylperoxy) -2,5-dimethylhexane (t-butylperoxy) -2,5-dimethylhexane was used in place of 0.54 parts by weight of the crosslinking agent t-butylperoxy 2-ethylhexylcarbonate Luperox 占 101, 1 hour half-life temperature: 140 占 폚) was used as a photopolymerization initiator to prepare a sheet-like encapsulant and a photovoltaic module.
Comparative Example One
A sheet-like encapsulant and a photovoltaic module were produced in the same manner as in Example 1, except that the crosslinking agent t-butylperoxy 2-ethylhexylcarbonate used in Example 1 and the crosslinking assistant triallyl isocyanurate were not used. .
Comparative Example 2
A sheet-like encapsulant and a photovoltaic module were produced in the same manner as in Example 1, except that the crosslinking agent t-butylperoxy 2-ethylhexylcarbonate used in Example 1 was not used.
(Content, density)
(Content wt%)
(Content wt%)
(Content wt%)
(d = 0.870)
0.54
(d = 0.870)
0.27
(d = 0.870)
0.054
(d = 0.870)
0.054
(d = 0.870)
0.54
(d = 0.870)
1.01
(d = 0.870)
0.009
(d = 0.870)
0.54
(d = 0.870)
(d = 0.870)
Experimental Example
1. Measurement of 90 degree peel strength
In order to measure the peel strength of the encapsulant produced in Examples 1 to 7 and Comparative Examples 1 and 2, a specimen similar to the manufactured photovoltaic module was separately prepared. The specimen 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 38 탆, polyethylene terephthalate having a thickness of 30 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. The lower glass plate of the manufactured specimen was fixed and the sealing material adhered to the backing sheet alone was peeled off at a stretching speed of 50 mm / min and a peeling angle of 90 degrees at the same time as a 15 mm wide rectangle in accordance with ASTM D1897 Peel strength is shown in Table 3 below.
2. Heat resistance durability evaluation
In order to evaluate the heat durability of the encapsulant prepared in Examples 1 to 5 and Comparative Examples 1 to 4, a specimen similar to the manufactured photovoltaic module was separately prepared. The test piece was a plate glass (thickness: about 8 mm), the above-prepared sealing material having a thickness of 500 μm was coated on a small plate glass (width x length = 12 mm x 12 mm, thickness: about 3 mm, weight about 140 g) Laminated in order of ash / large plate glass, and laminated in a vacuum laminator at 150 DEG C for 17 minutes. The prepared specimens were stored in an oven at 100 ° C for 10 hours at an angle of 90 °, and then the slip length of the small plate glass was measured to evaluate creep characteristics.
The evaluation criteria were as follows, and the evaluation results are shown in Table 2 below.
<Evaluation Criteria>
○: no phenomenon that the sealing material flows down was observed at all
B: Partially observed phenomenon of the sealing material flowing down
Ⅹ: The phenomenon that the sealing material flows down is observed.
(N / 15 mm)
1, 2: Solar cell module
11, 21: front substrate
12, 22: back sheet
13, 23: photovoltaic element
14 (a), 14 (b), 24: Encapsulation material
Claims (20)
[Chemical Formula 1]
DSiR 1 p R 2 (3-p)
In Formula 1, D represents alkenyl bonded to a silicon atom,
R 1 represents a hydroxyl group, halogen, an amine group or -R 3 R 4 bonded to a silicon atom,
R 3 is an oxygen or sulfur atom,
R 4 represents an alkyl group, an aryl group or an acyl group,
R 2 represents hydrogen, an alkyl group, an aryl group or an aralkyl group bonded to a silicon atom,
p is an integer of 1 to 3;
Adding a crosslinking agent and a crosslinking assistant to the silane-modified olefin resin, and molding the resultant into a film or a sheet form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130115212A KR20150035075A (en) | 2013-09-27 | 2013-09-27 | Olefin resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130115212A KR20150035075A (en) | 2013-09-27 | 2013-09-27 | Olefin resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150035075A true KR20150035075A (en) | 2015-04-06 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR20130115212A KR20150035075A (en) | 2013-09-27 | 2013-09-27 | Olefin resin composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20150035075A (en) |
-
2013
- 2013-09-27 KR KR20130115212A patent/KR20150035075A/en not_active Application Discontinuation
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