CN104380481B - Solar cell sealing material and solar cell module - Google Patents

Solar cell sealing material and solar cell module Download PDF

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Publication number
CN104380481B
CN104380481B CN201380031931.1A CN201380031931A CN104380481B CN 104380481 B CN104380481 B CN 104380481B CN 201380031931 A CN201380031931 A CN 201380031931A CN 104380481 B CN104380481 B CN 104380481B
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Prior art keywords
solar cell
sealing material
cell sealing
alpha
weight portion
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CN104380481A (en
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池永成伸
竹内文人
伊藤智章
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Mitsui Chemicals Tohcello Inc
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Mitsui Chemicals Tohcello Inc
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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

This solar cell sealing material contains an ethylene-alpha-olefin copolymer, an organic peroxide and an ultraviolet absorbent, and the ultraviolet absorbent is a benzotriazole-based ultraviolet absorbent that is represented by general formula (1) or (2). (In general formula (1), R1 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms; and R2-R4 may be the same or different, and each represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, a hydroxyl group, an alkoxy group having 1-22 carbon atoms or an alkyloxycarbonyl group having 1-22 carbon atoms.) (In general formula (2), R1 represents the above-mentioned substituent; and R5-R8 may be the same or different, and each represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, a hydroxyl group, an alkoxy group having 1-22 carbon atoms or an alkyloxycarbonyl group having 1-22 carbon atoms.)

Description

Solar cell sealing material and solar module
Technical field
The present invention relates to solar cell sealing material and solar module.
Background technology
During the seriousness of global environmental problems, energy problem etc. increases, as clean and be not concerned about exhaustion The energy generates means, and solaode receives publicity.By solaode building the outdoor application such as roof parts In the case of, typically used in the form of solar module.
Above-mentioned solar module, it is however generally that, manufactured by following steps.First, manufacture passes through polycrystalline The crystal type solar cell device of the formation such as silicon, monocrystalline silicon (below, is expressed as generating element or unit.), or will be without fixed Shape silicon, silicon metal etc. form thin film solar cell element obtained from several μm of very thin film on the substrates such as glass Deng.
Next, in order to obtain crystal type solar module, according to solar module screening glass (face side Transparent protection member)/solar cell sealing material/crystal type solar cell device/solar cell sealing material/solar-electricity Pond module carries out lamination with the order of screening glass (rear side protection component).
On the other hand, in order to obtain thin film solar cell module, according to thin film solar cell element/solar energy The order of cell sealing material/solar module screening glass (rear side protection component) carries out lamination.Then, by using By their evacuation and laminating etc. of thermo-compression bonding is added to manufacture solar module.The solaode mould for so manufacturing Block has against weather, is also suitable for the outdoor application such as roof parts in building.
As solar cell sealing material, vinyl-vinyl acetate copolymer (EVA) film due to the transparency, flexibility and Cementability etc. is excellent, therefore is widely used.Wherein, as the solar-electricity that can for a long time maintain excellent ultraviolet barrier Pond diaphragm seal, it is proposed that comprising vinyl-vinyl acetate copolymer, organic peroxide and enumerate BTA system UV absorbent Solar cell sealing film (with reference to patent documentation 1).However, using EVA compositionss as solar cell sealing material During constituent material, worry that the compositions such as the acetic acid gas that EVA decomposes and produces bring the possibility of impact on solar cell device Property.
On the other hand, it is proposed that the sun being made up of ethene-alpha-olefin copolymer, organic peroxide and silane coupler Can cell sealing timber-used resin combination (for example, referring to patent documentation 2).It is said that the solar cell sealing timber-used resin combination The thermostability of thing, the transparency, flexibility and to the excellent in adhesion of glass substrate.
Additionally, the exploitation of solar cell device is also actively carried out, as the solar cell device of high conversion efficiency, By the long wavelength region near the 400～1300nm of amorphous silicon and absorption of the light for absorbing the short wavelength region near 300～700nm Tandem type solar cell device obtained by the crystal type silicon lamination of the light in domain just circulates in the market.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2011-201928 publications
Patent documentation 2：No. 2010/114028 pamphlet of International Publication No.
The content of the invention
Invent problem to be solved
However, the present inventor etc. has found, although the solar cell sealing timber-used resin combination described in patent documentation 2 Cementability is abundant, but against weather is insufficient, transparent poor, the tandem type solaode near particularly wavelength 500nm Module has the tendency of that conversion efficiency can not be favorably improved.
Therefore, problem of the invention is to provide that against weather is excellent, also maintains light transmission after prolonged ultraviolet irradiation The solar cell sealing material of property.
Means for solving the problems
The present inventor etc. has been repeated further investigation to against weather.Its result is to find, purple containing enumerate BTA system Ultraviolet absorbers, the solar cell sealing material comprising ethene-alpha-olefin copolymer, against weather is excellent, prolonged purple Photopermeability is also maintained after outside line irradiation, so as to complete the present invention.
That is, according to the present invention, there is provided solar cell sealing material shown below.
[1]
A kind of solar cell sealing material, it is characterised in that be comprising ethene-alpha-olefin copolymer, organic peroxide With the solar cell sealing material of UV absorbent,
Enumerate BTA system UV absorbent of the above-mentioned UV absorbent shown in following formulas (1) or (2).
(in formula, R1Represent the alkyl of hydrogen atom or carbon number 1～6, R2～R4Can be the same or different, represent The alkyl oxygen of hydrogen atom, the alkyl of carbon number 1～20, hydroxyl, the alkoxyl of carbon number 1～22 or carbon number 1～22 Base carbonyl.)
(in formula, R1Represent the alkyl of hydrogen atom or carbon number 1～6, R5～R8Can be the same or different, represent The alkyl oxygen of hydrogen atom, the alkyl of carbon number 1～20, hydroxyl, the alkoxyl of carbon number 1～22 or carbon number 1～22 Base carbonyl.)
[2]
Solar cell sealing material according to [1], it is characterised in that in above-mentioned formula (1), R1Represent that hydrogen is former Son, R2～R4It is mutually different.
[3]
Solar cell sealing material according to [1] or [2], it is characterised in that in above-mentioned formula (2), R1Represent Hydrogen atom, R5With R8It is identical, R6With R7It is identical.
[4]
Solar cell sealing material according to any one of [1]～[3], the above-mentioned purple in solar cell sealing material The content of ultraviolet absorbers, is 0.05～5.0 weight portion relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100.
[5]
Solar cell sealing material according to any one of [1]～[4], above-mentioned ethene-alpha-olefin copolymer meets Following important document a1)～a4).
A1) content ratio from the Component units of ethylene is 80～90mol%, from carbon number 3～20 The content ratio of the Component units of alpha-olefin is 10～20mol%.
A2) according to ASTM D1238, it is 10～50g/10 that the MFR for obtaining is determined under conditions of 190 DEG C, 2.16kg loadings Minute.
A3 it is 0.865～0.884g/cm that the density for obtaining) is determined according to ASTM D15053。
A4 it is 60～85 that the Xiao A hardness for obtaining) is determined according to ASTM D2240.
[6]
Solar cell sealing material according to any one of [1]～[5], according to ASTM D1238,190 DEG C, The MFR that the above-mentioned ethene-alpha-olefin copolymer for obtaining is determined under conditions of 2.16kg loadings is 10～27g/10 minutes.
[7]
Solar cell sealing material according to any one of [1]～[6], 1 minute half of above-mentioned organic peroxide The phase temperature that declines is 100～170 DEG C, and the content of above-mentioned organic peroxide, relative to above-mentioned ethene-alpha-olefin copolymer 100 weight portions are 0.1～3 weight portion.
[8]
Solar cell sealing material according to any one of [1]～[7], it further includes silane coupler,
The content of above-mentioned silane coupler, is 0.1～5 weight relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100 Amount part.
[9]
Solar cell sealing material according to any one of [1]～[8], it is further stable comprising hindered phenol series Agent,
The content of above-mentioned hindered phenol series stabilizer, is 0.005 relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100 ～0.1 weight portion.
[10]
Solar cell sealing material according to any one of [1]～[9], it further stablizes comprising the amine system light that is obstructed Agent,
The content of the above-mentioned amine system light stabilizer that is obstructed, is 0.01 relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100 ～2.0 weight portions.
[11]
Solar cell sealing material according to any one of [1]～[10], it further includes phosphorus system stabilizer,
The content of above-mentioned phosphorus system stabilizer, is 0.005～0.5 relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100 Weight portion.
[12]
Solar cell sealing material according to any one of [1]～[11], it further includes crosslinking coagent,
The content of above-mentioned crosslinking coagent, is 0.05～5 weight relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100 Part.
[13]
Solar cell sealing material according to any one of [1]～[12], it is by above-mentioned ethene-alpha-olefin copolymerization After thing, above-mentioned organic peroxide and above-mentioned UV absorbent melting mixing, lamellar ground extrusion molding and obtain.
[14]
Solar cell sealing material according to any one of [1]～[13], it is lamellar.
[15]
A kind of solar module, it possesses：
Face side transparent protection member,
Rear side protects component,
Solar cell device, and
Sealant, the sealant is that the solar cell sealing material described in any one for making [1]～[14] is crosslinked and shape Into, and by above-mentioned solar cell device be sealed in above-mentioned face side transparent protection member and above-mentioned rear side protection component it Between.
[16]
Solar module according to [15], above-mentioned solar cell device is to fold silicon metal with amorphous silicon Layer.
The effect of invention
According to the present invention it is possible to provide that against weather is excellent, also maintain photopermeability after the irradiation of prolonged ultraviolet Solar cell sealing material.
According to the present invention, by using such solar cell sealing material, can provide except above-mentioned each characteristic is excellent Beyond different, the excellent solar module of the economy such as the outward appearance of solaode, cost is not damaged yet.
The solar cell sealing material of the present invention can be in crystal type solar module, thin film solar cell mould Used in block, the whole of tandem type solar module, but particularly can be provided in tandem type solar cell device The raising of without prejudice to conversion efficiency and the excellent solar module of the economy such as cost.
Description of the drawings
Above-mentioned purpose and other objects, features and advantages by the preferred implementation of described below and its it is appended with Lower accompanying drawing comes further clearly.
Fig. 1 is the sectional view of an embodiment of the solar module for schematically showing the present invention.
Fig. 2 is the plane graph of a configuration example at the sensitive surface and back side for schematically showing solar cell device.
Specific embodiment
Hereinafter, embodiments of the present invention are illustrated using accompanying drawing.In addition, in whole accompanying drawings, to same structure Same symbol is enclosed into key element, is suitably omitted the description.Additionally, with regard to "～", if do not specialized, then it represents that with up to Below.
1. with regard to solar cell sealing material
(ethene-alpha-olefin copolymer)
Ethene-alpha-olefin copolymer used by the solar cell sealing material of present embodiment is by by ethylene and carbon atom The alpha-olefin of number 3～20 carries out copolymerization to obtain.As alpha-olefin, generally can be used alone the α of carbon number 3～20- Alkene is applied in combination two or more.As the alpha-olefin of carbon number 3～20, the α-alkene of straight-chain or branched can be enumerated Hydrocarbon, for example, propylene, 1-butylene, 1- amylenes, 1- hexenes, 3-methyl-1-butene, 3,3- dimethyl -1-butylene, 4- methyl-1-pentenes Alkene, 1- octenes, 1-decene, 1- dodecylenes etc..The alpha-olefin that carbon number is less than 10 is wherein it is preferred that, it is particularly preferred It is alpha-olefin that carbon number is 3～8.Consider to be preferably propylene, 1-butylene, 1- amylenes, 1- hexenes, 4- from the easiness for obtaining Methyl-1-pentene and 1- octenes.
In addition, ethene-alpha-olefin copolymer can be random copolymer, or block copolymer, but from flexibility From the viewpoint of be preferably random copolymer.
Additionally, the ethene-alpha-olefin copolymer used by the solar cell sealing material of present embodiment can be ethylene, carbon The copolymer that the alpha-olefin of atomic number 3～20 and unconjugated polyene are formed.Alpha-olefin as described above, as non-conjugated many Alkene, can enumerate 5-ethylidene-2-norbornene (ENB), 5- vinyls -2- norborene (VNB), bicyclopentadiene (DCPD) Deng.These unconjugated polyenes can be used alone, or two or more is applied in combination.
Ethene-alpha-olefin copolymer used by the solar cell sealing material of present embodiment can be used together aromatic vinyl Based compound, for example, styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, neighbour, p- dimethyl benzene second It is alkene, methoxy styrene, vinyl benzoic acid, vinylbenzoate, vinyl benzyl yl acetate, hydroxy styrenes, right The phenylethylenes such as chlorostyrene, divinylbenzene；3- phenylpropens, 4- phenylpropens, α-methyl styrene, carbon number are 3 ～20 cyclic olefin such as cyclopentenes, cycloheptene, norborene, 5- methyl -2- norborene etc..
The solar cell sealing material of present embodiment preferably further meets following important document a1～a4.
(important document a1)
The content ratio of the Component units from ethylene that ethene-alpha-olefin copolymer is included is preferably 80～ 90mol%, more preferably 80～88mol%, more preferably 82～88mol%, particularly preferably 82～87mol%.Second Component units (hereinafter, also referred to as " the α-alkene of the alpha-olefin from carbon number 3～20 that alkene-alpha olefin copolymer is included Hydrocarbon unit ") content ratio be preferably 10～20mol%, more preferably 12～20mol%, more preferably 12～ 18mol%, particularly preferably 13～18mol%.
If the content ratio of the alpha-olefin unit that ethene-alpha-olefin copolymer is included is more than 10mol%, can obtain Obtain the high transparency.Furthermore, it is possible to easily carry out the extrusion molding under low temperature, for example, can realize less than 130 DEG C of extrusion Molding.Therefore, even if in the case of refining organic peroxide in ethene-alpha-olefin copolymer, it is also possible to suppress extruder The carrying out of interior cross-linking reaction, can prevent the gelatinous foreign body of piece generation of solar cell sealing material and the outward appearance of piece is disliked Change.Further, since appropriate flexibility can be obtained, thus can prevent solar module it is laminated into type when occur too Cracking, defect of membrane electrode of positive energy cell device etc..
If the content ratio of the alpha-olefin unit that ethene-alpha-olefin copolymer is included is below 20mol%, second The crystallization rate of alkene-alpha olefin copolymer becomes appropriateness, therefore the piece from extruder extrusion will not be tacky, the stripping on chill roll Easily, the piece of the solar cell sealing material of lamellar can be effectively obtained.Further, since piece do not occur it is tacky, therefore can be with Preventing the stretching out property of adhesion, piece becomes good.In addition it is also possible to prevent the reduction of thermostability.
(important document a2)
According to ASTM D1238, the ethene-alpha-olefin copolymer for obtaining is determined under conditions of 190 DEG C, 2.16kg loadings Melt flow rate (MFR) (MFR) be usually 0.1～50g/10 minutes, more preferably preferably 2～50g/10 minutes, 10～50g/ 10 minutes, more preferably 10～40g/10 minutes, particularly preferably 12～27g/10 minutes, most preferably 15～25g/10 Minute.The MFR of ethene-alpha-olefin copolymer can pass through adjust polyreaction described later when polymerization temperature, polymerization pressure, with And the monomer concentration of the ethylene in polymerization system and alpha-olefin and the molar ratio of hydrogen concentration etc. are adjusting.
(calendering formation)
If MFR is 0.1g/10 minutes less than 10g/10 minutes, piece can be manufactured by calendering formation. If MFR is 0.1g/10 minutes less than 10g/10 minutes, the resin combination comprising ethene-alpha-olefin copolymer Mobility it is low, therefore layer caused by the molten resin institute oozed out when preventing and be laminated piece and solar cell device The pollution aspect of pressure device is preferably.
(extrusion molding)
Additionally, if MFR is 2g/10 more than minute, preferred MFR is 10g/10 more than minute, then comprising ethene-alpha-olefin The mobility of the resin combination of copolymer is improved, and improves can productivity during piece extrusion molding.
If MFR is below 50g/10 minutes, molecule quantitative change is big, therefore can suppress the attached of the roll surface to chill roll etc. , therefore need not peel off, the piece of uniform thickness can be shaped to.Further, since the resin combination with " hardness " is formed, Therefore can easily more than molding 0.1mm sheet.Further, since solar module it is laminated into type when crosslinking it is special Property improve, therefore it can be made fully to be crosslinked, suppress the reduction of thermostability.
If MFR is below 27g/10 minutes, can further suppress drawdown during sheetmolding, can be with forming width width Piece, and crosslinking feature and thermostability further improve, it is possible to obtain most good solar cell sealing material piece.
In addition, not carrying out the feelings of the crosslinking Treatment of resin combination in the lamination of solar module described later Under condition, the impact of the decomposition of organic peroxide is little in melting extrusion operation, therefore can also the use of MFR be 0.1g/10 minutes Less than 10g/10 minutes, preferably 0.5g/10 minutes, less than the resin combination of 8.5g/10 minutes, pass through Extrusion molding is obtaining piece.In the case where the organic peroxide content of resin combination is for below 0.15 weight portion, also may be used The use of MFR to be resin combination of the 0.1g/10 minutes less than 10g/10 minutes, silane-modified process or micro- is being carried out Forming temperature while crosslinking Treatment at 170～250 DEG C manufactures piece by extrusion molding.If MFR is within the range, In terms of the pollution of the caused laminater of molten resin institute oozed out when preventing and be laminated piece and solar cell device It is preferred.
(important document a3)
The density for determining the ethene-alpha-olefin copolymer for obtaining according to ASTM D1505 is preferably 0.865～0.884g/ cm3, more preferably 0.866～0.883g/cm3, more preferably 0.866～0.880g/cm3, particularly preferably 0.867～ 0.880g/cm3.The density of ethene-alpha-olefin copolymer, can be by the content ratio of ethylene unit and containing for alpha-olefin unit Proportional balance is adjusting.That is, if improving the content ratio of ethylene unit, crystallinity is uprised, it is possible to obtain density is high Ethene-alpha-olefin copolymer.On the other hand, if reducing the content ratio of ethylene unit, crystallinity step-down can be obtained Obtain low density ethene-alpha-olefin copolymer.
If the density of ethene-alpha-olefin copolymer is 0.884g/cm3Hereinafter, then crystallinity step-down, can improve transparent Property.Additionally, the extrusion molding under low temperature becomes easy, for example, extrusion molding can be carried out below 130 DEG C.Therefore, even if in second Refine in alkene-alpha olefin copolymer into organic peroxide, it is also possible to prevent the carrying out of the cross-linking reaction in extruder, can suppress The piece of solar cell sealing material produces gelatinous foreign body, suppresses the deteriorated appearance of piece.Further, since flexibility is high, therefore Can prevent solar module it is laminated into type when occur as solar cell device unit cracking, thin-film electro Defect of pole etc..
On the other hand, if the density of ethene-alpha-olefin copolymer is 0.865g/cm3More than, then can accelerate ethylene- The crystallization rate of alpha olefin copolymer, therefore be difficult from the piece of extruder extrusion tacky, stripping on chill roll becomes easy, can be with It is readily available the piece of solar cell sealing material.Further, since piece be not susceptible to it is tacky, therefore can suppress adhesion send out Raw, the stretching out property for making piece is improved.Further, since being fully crosslinked, therefore the reduction of thermostability can be suppressed.
(important document a4)
The Xiao A hardness of ethene-alpha-olefin copolymer for obtaining is determined according to ASTM D2240 and is preferably 60～85, it is more excellent Elect 62～83, more preferably 62～80, particularly preferably 65～80 as.The Xiao A hardness of ethene-alpha-olefin copolymer can With by the way that the content ratio of the ethylene unit of ethene-alpha-olefin copolymer, density domination are adjusted in above-mentioned numerical range. That is, the Xiao A hardness of the ethene-alpha-olefin copolymer that content ratio is high, density is high of ethylene unit is uprised.On the other hand, second The content ratio of alkene unit is low, low density ethene-alpha-olefin copolymer Xiao A hardness step-down.
If Xiao A hardness is more than 60, ethene-alpha-olefin copolymer becomes to be difficult tacky, can suppress adhesion.This Outward, when solar cell sealing material is processed as into lamellar, it is also possible to which the stretching out property for making piece is improved, and can also suppress thermostability Reduce.
On the other hand, if Xiao A hardness is less than 85, crystallinity step-down can improve the transparency.Further, since Flexibility is high, thus can prevent solar module it is laminated into type when open as the unit of solar cell device Split, the breakage of membrane electrode etc..
Additionally, the solar cell sealing material of present embodiment, it is also preferred mode further to meet following important document.
(melting peak)
Ethene-alpha-olefin copolymer, based on means of differential scanning calorimetry determine (DSC) melting peak be preferably in 30～90 DEG C scope, be further preferably present in 33～90 DEG C of scope, be particularly preferably present in 33～88 DEG C of scope.If melting Peak is less than 90 DEG C, then degree of crystallinity step-down, the flexibility raising of the solar cell sealing material of gained, thus it is laminated into type too Cracking, the defect of membrane electrode of unit can be prevented during positive energy battery module.On the other hand, if melting peak is 30 DEG C More than, then the flexibility of resin combination can be moderately improved, therefore solar energy can be readily available by extrusion molding Cell sealing material piece.Furthermore, it is possible to prevent by the tacky adhesion for causing of piece, the deterioration of the stretching out property of suppression piece.
(volume intrinsic resistance)
The solar cell sealing material of present embodiment, according to JIS K6911, is surveyed with 100 DEG C of temperature, applied voltage 500V Surely the volume intrinsic resistance for obtaining is preferably 1.0 × 1013～1.0 × 1018Ω·cm.The big solar-electricity of volume intrinsic resistance Pond sealing material has the tendency of that there is suppression PID phenomenons such characteristic to occur.Additionally, in the time-bands of irradiation sunlight, for For conventional solar module, module temperature is changed into such as more than 70 DEG C sometimes, therefore from the viewpoint of long-term reliability Consider, compared with the volume intrinsic resistance under the room temperature (23 DEG C) of conventional report, more require that the volume under the conditions of high temperature is inherently electric Resistance, the volume intrinsic resistance of 100 DEG C of temperature becomes important.
According to JIS K6911, (below, the volume intrinsic resistance for obtaining is determined with 100 DEG C of temperature, applied voltage 500V Referred to as " volume intrinsic resistance ".) it is more preferably 1.0 × 1014～1.0 × 1018Ω cm, more preferably 5.0 × 1014 ～1.0 × 1018Ω cm, particularly preferably 1.0 × 1015～1.0 × 1018Ω·cm.As fruit volume intrinsic resistance be 1.0 × 1013More than Ω cm, then can also suppress 1 day or so PID in a short time to show in the constant temperature and moisture test under 85 DEG C, 85%rh The generation of elephant.If fruit volume intrinsic resistance is 1.0 × 1018Below Ω cm, then piece become to be not likely to produce electrostatic, therefore can in case The only absorption of pollutant, can suppress to be mixed into pollutant in solar module and cause generating efficiency, long-term reliability Reduction.
In addition, if volume intrinsic resistance is 5.0 × 1014More than Ω cm, the then constant temperature and humidity under 85 DEG C, 85%rh There is to make the generation of PID phenomenons further to extend in test, thus it is preferred that.Volume intrinsic resistance be be shaped to it is close After envelope material piece, it is crosslinked with vacuum laminator, hot press, crosslinking stove etc. and is processed into what is determined after flat piece.Additionally, module is folded Piece in layer body is determined after other layers are removed.
(content of aluminium element)
The content of the aluminium element (hereinafter, also referred to as " Al ") that ethene-alpha-olefin copolymer is included is preferably 10～ 500ppm, more preferably 20～400ppm, more preferably 20～300ppm.Al content depends on common in ethene-alpha-olefin Organoalurrunoxy compound, the concentration of organo-aluminum compound added in the polymerization process of polymers.
In the case where Al content is more than 10ppm, that what is added in the polymerization process of ethene-alpha-olefin copolymer is organic The concentration of the degree that aluminum oxide, organo-aluminum compound can be showed fully with the activity of Metallocenic compound is added Plus, therefore need not add with Metallocenic compound react and formed ion pair compound.Adding the formation ion pair In the case of compound, sometimes the compound of the formation ion pair is remained in ethene-alpha-olefin copolymer, so as to cause electrically The reduction (electrical characteristic having the tendency of under for example waiting high temperature at 100 DEG C is reduced) of characteristic, but it is prevented from such phenomenon.This Outward, in order to reduce Al content, need to carry out deliming process with acid, alkali, remain in rewarding ethene-alpha-olefin copolymer Acid, alkali cause the tendency of the corrosion of electrode, process to implement deliming, and the cost of ethene-alpha-olefin copolymer is also uprised, but not Such deliming is needed to process.
Additionally, if Al content is below 500ppm, the carrying out of the cross-linking reaction in extruder can be prevented, therefore can Producing gel foreign body with the piece for preventing solar cell sealing material causes the deteriorated appearance of piece.
Method as the aluminium element that ethene-alpha-olefin copolymer as described above is included is controlled, for example, by adjustment (II-1) organoalurrunoxy compound and (II-2) organic calorize described in the manufacture method of ethene-alpha-olefin copolymer described later The polymerization activity of the Metallocenic compound of the manufacturing condition of concentration or ethene-alpha-olefin copolymer of the compound in manufacturing process, The aluminium element that ethene-alpha-olefin copolymer is included can be controlled.
(manufacture method of ethene-alpha-olefin copolymer)
Ethene-alpha-olefin copolymer can be by using conducts such as Ziegler compound, vfanadium compound, Metallocenic compounds Catalyst is manufacturing.Various Metallocenic compounds shown below are wherein preferably used as the catalyst to manufacture.As metal Cyclopentadinyl compound, it is, for example possible to use Japanese Unexamined Patent Publication 2006-077261 publications, Japanese Unexamined Patent Publication 2008-231265 publications, day Metallocenic compound described in this JP 2005-314680 publications etc..It is also possible, however, to use with these patent documentation institutes The Metallocenic compound of the Metallocenic compound different structure of record, it is also possible to be applied in combination more than two kinds Metallocenic compounds.
As the polyreaction using Metallocenic compound, form for example shown below can be enumerated as suitable examples.
(II-1) organoalurrunoxy compound, (II- are being selected from comprising known Metallocenic compound and (II) 2) compound and (II-3) organo-aluminum compound for reacting with above-mentioned Metallocenic compound (I) and forming ion pair is constituted In the presence of the catalyst for olefines polymerizing of at least one compound (also referred to as promoter) in group, supply ethylene and be selected from The monomer of one or more of alpha-olefin etc..
React with above-mentioned Metallocenic compound (I) as (II-1) organoalurrunoxy compound, (II-2) and form ion pair Compound and (II-3) organo-aluminum compound, for example, it is also possible to special using Japanese Unexamined Patent Publication 2006-077261 publications, Japan Open the Metallocenic compound described in 2008-231265 publications and Japanese Unexamined Patent Publication 2005-314680 publications etc..However, The Metallocenic compound with the Metallocenic compound different structure described in these patent documentations can be used.These compounds can Put in polymerization atmosphere with independent or advance contact.Additionally, for example can also support in Japanese Unexamined Patent Publication 2005-314680 Inorganic particulate oxide carrier described in publication etc. and use.
Additionally, it is preferred that formed by substantially not using above-mentioned (II-2) and above-mentioned Metallocenic compound (I) to react from Son to compound manufacturing, it is possible to obtain the ethene-alpha-olefin copolymer of excellent electrical characteristic.
React with above-mentioned Metallocenic compound (I) as (II-2) and form the compound of ion pair (below, sometimes referred to as For " ionic compound (II) ".), Japanese Unexamined Patent Publication 1-501950 publication, Japanese Unexamined Patent Publication No. 1-502036 number can be enumerated Publication, Japanese Unexamined Patent Publication 3-179005 publication, Japanese Unexamined Patent Publication 3-179006 publication, Japanese Unexamined Patent Publication 3-207703 public affairs Report, Japanese Unexamined Patent Publication 3-207704 publication, lewis acid, ionic compound, borine described in No. USP5321106 etc. Compound and caborane compounds etc..Additionally, as ionic compound (II), it is also possible to enumerate heteropoly compound and different polyvoltine Compound.
The polymerization of ethene-alpha-olefin copolymer can be by known gaseous polymerization, slurry polymerization process, Yi Jirong Any one in the liquid polymerizations such as liquid polymerization is carrying out.It is preferred that being carried out by liquid polymerizations such as solution polymerization process. Using Metallocenic compound as described above, carry out ethylene and the copolymerization of the alpha-olefin of carbon number 3～20 and manufacture ethylene-α- In the case of olefin copolymer, Metallocenic compound (I) per 1 liter of reaction volume being usually 10-9～10-1Mole, preferably 10-8～10-2Measure to use as mole.
Compound (II-1) is with the mol ratio of the whole transition metal atoms (M) in compound (II-1) and compound (I) [(II-1)/M] is usually 1～10000, preferably 10～5000 such amounts to use.Compound (II-2) with compound (I) mol ratio [(II-2)/M] of the whole transition metal (M) in is usually 0.5～50, preferably 1～20 such amount to make With.Compound (II-3) is usually 0～5 mM with the volume that is polymerized per 1 liter, measures to make as preferably from about 0～2 mM With.
In solution polymerization process, in the presence of Metallocenic compound as described above, by carrying out ethylene and carbon number 3 The copolymerization of～20 alpha-olefin, can efficiently manufacture co-monomer content height, constitute narrowly distributing, the second of narrow molecular weight distribution Alkene-alpha olefin copolymer.Here, ethylene is usually ethylene with the addition mol ratio of the alpha-olefin of carbon number 3～20:Alpha-olefin =10:90～99.9:0.1, preferably ethylene:Alpha-olefin=30:70～99.9:0.1, more preferably ethylene:Alpha-olefin =50:50～99.9:0.1.
So-called " solution polymerization process ", is to be dissolved with the state of polymer to be polymerized in nonactive hydrocarbon solvent described later Method general name.Polymerization temperature in solution polymerization process is usually 0～200 DEG C, preferably 20～190 DEG C, further preferably For 40～180 DEG C.In solution polymerization process, in the case where polymerization temperature is less than 0 DEG C, its polymerization activity is terrifically reduced, and is gathered Closing the heat extraction of heat also becomes difficult, impracticable from from the aspect of productivity.If additionally, polymerization temperature is polymerized more than 200 DEG C Activity is terrifically reduced, therefore impracticable from from the aspect of productivity.
Polymerization pressure is usually normal pressure～10MPa gauge pressures, preferably under conditions of normal pressure～8MPa gauge pressures.Copolymerization can lead to The either method crossed in batch (-type), semi continuous, continuous way is carried out.Response time (is implemented in copolyreaction by continuity method In the case of, it is mean residence time) according to the different and different of the conditions such as catalyst concn, polymerization temperature, can suitably select, But usually 1 minute～3 hours, preferably 10 minutes～2.5 hours.It is further possible to be divided into reaction condition different 2 sections with On be polymerized.The molecular weight of the ethene-alpha-olefin copolymer of gained can also pass through to change hydrogen concentration in polymerization system, poly- Close temperature to adjust.In addition it is also possible to pass through the amount of used compound (II) to adjust.In the case of addition hydrogen, close Yu Qiliang, it is appropriate that the ethene-alpha-olefin copolymer generated per 1kg is 0.001～5,000NL or so.Additionally, there are in institute The vinyl and ethenylidene of the molecular end of the ethene-alpha-olefin copolymer for obtaining can be by improving polymerization temperature, strongly subtracting Less plus hydrogen amount is adjusting.
Solvent used in solution polymerization process is usually nonactive hydrocarbon solvent, preferably the boiling point under normal pressure be 50 DEG C～ 200 DEG C of saturated hydrocarbons.Specifically, the aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene can be enumerated； The clicyclic hydrocarbons such as Pentamethylene., hexamethylene, methyl cyclopentane.In addition, benzene,toluene,xylene etc. is aromatic hydrocarbon；Ethlyene dichloride, The halogenated hydrocarbons such as chlorobenzene, dichloromethane also fall into the category of " nonactive hydrocarbon solvent ", do not limit it and use.
As described above, in solution polymerization process, the in the past conventional organo-aluminium for being dissolved in aromatic hydrocarbon not only can be used Oxygen compound, and the modified methylaluminoxane as MMAO for being dissolved in aliphatic hydrocarbon, clicyclic hydrocarbon can also be used.Its If as a result, adopting aliphatic hydrocarbon, clicyclic hydrocarbon as the solvent of polymerisation in solution, almost can exclude completely poly- The probability of aromatic hydrocarbon is mixed in zoarium system, in the ethene-alpha-olefin copolymer of generation.That is, solution polymerization process also have can To mitigate carrying capacity of environment, the impact to health can be made to minimize such feature.In addition, in order to suppress physics value not Uniformly, preferably by the ethene-alpha-olefin copolymer obtained by polyreaction and other compositions being added as needed on by any Method melting, implement mixing, pelletize etc..
(organic peroxide)
The solar cell sealing material of present embodiment includes organic peroxide.Organic peroxide is used as silane coupled The radical initiator during graft modification of agent and ethene-alpha-olefin copolymer and as ethene-alpha-olefin copolymer too It is positive can battery module it is laminated into type when cross-linking reaction when radical initiator and use.By common to ethene-alpha-olefin Polymers graft modification silane coupler, can obtain and face side transparent protection member, rear side protection component, unit, electrode The good solar module of cementability.Additionally, passing through cross-linked ethylene-alpha olefin copolymer, it is possible to obtain thermostability, bonding The excellent solar module of property.
As long as the organic peroxide for preferably using can be silane coupled to ethene-alpha-olefin copolymer graft modification Agent or the organic peroxide of cross-linked ethylene-alpha olefin copolymer, are not particularly limited, but the life from extrusion sheetmolding Produce property with solar module it is laminated into type when crosslinking rate balance consider, 1 minute half of organic peroxide is declined Phase temperature is preferably 100～170 DEG C.If 1 minute half life temperature of organic peroxide is more than 100 DEG C, in extrusion The solar cell sealing piece obtained by resin combination during sheetmolding becomes to be not likely to produce gel, therefore can suppress extruder Torque rising and make sheetmolding easy.Further, since can suppress because of the jello of generation in extruder in piece Surface generation is concavo-convex, therefore can prevent deteriorated appearance.Additionally, in applied voltage, due to opening inside anti-limited step Split, therefore the reduction of breakdown voltage can be prevented.In addition it is also possible to prevent the reduction of poisture-penetrability.Further, since can press down System piece surface produce it is concavo-convex, therefore in the lamination process of solar module with face side transparent protection member, unit, Electrode, the adaptation of rear side protection component become good, and cementability is also improved.If by the extrusion temperature of extrusion sheetmolding Be reduced to less than 90 DEG C, although then can molding, productivity is greatly lowered.If 1 minute half of organic peroxide declines Phase temperature is less than 170 DEG C, then can suppress solar module it is laminated into type when crosslinking rate reduction, therefore can To prevent the productive reduction of solar module.In addition it is also possible to prevent the thermostability of solar cell sealing material, glue The reduction of connecing property.
As organic peroxide, it is possible to use known organic peroxide.As 1 minute half life temperature 100 The preferred concrete example of the organic peroxide in the range of～170 DEG C, can enumerate dilauroyl peroxide, 1,1,3,3- tetramethyl Butyl peroxy -2-ethylhexanoate, diperoxy benzoyl, t-amyl peroxy -2-ethylhexanoate, t-butyl peroxy Change -2-ethylhexanoate, tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide the maleate, (t-amyl peroxies of 1,1- bis- Change) -3,3,5- trimethyl-cyclohexanes, 1,1- bis- (t-amyl peroxy) hexamethylene, t-amyl peroxy isononoate, tertiary pentyl Peroxidating caprylic acid ester, 1,1- bis- (tert-butyl hydroperoxide) -3,3,5- trimethyl-cyclohexanes, 1,1- bis- (tert-butyl hydroperoxide) ring Hexane, t-butylperoxyisopropyl carbonic ester, tert-butyl hydroperoxide -2- ethylhexyl carbonates, 2,5- dimethyl -2,5- two (benzoyl peroxidating) hexane, t-amyl peroxy benzoate, tert-butyl hydroperoxide acetass, the different n-nonanoic acid of tert-butyl hydroperoxide Ester, 2,2- bis- (tert-butyl hydroperoxide) butane, tert butyl peroxy benzoate etc..Preferably dilauroyl peroxide, tertiary fourth Base isopropyl peroxide carbonic ester, tert-butyl hydroperoxide acetass, tert-butyl hydroperoxide isononoate, tert-butyl hydroperoxide -2- Ethylhexyl carbonate, tert butyl peroxy benzoate etc..Above-mentioned organic peroxide can be used alone one kind, it is also possible to Two kinds mixed above to use.
The content of the organic peroxide in solar cell sealing material, relative to above-mentioned ethene-alpha-olefin copolymer 100 weight portions, preferably 0.1～3 weight portion, more preferably 0.2～3 weight portion, particularly preferably 0.2～2.5 weight portion.
If the content of organic peroxide is more than 0.1 weight portion, the friendship of solar cell sealing material can be suppressed The reduction of the crosslinking features such as connection degree, crosslinking rate, makes silane coupler good to the graft reaction of the main chain of vinyl copolymer It is good, suppress thermostability, the reduction of cementability.
If the content of organic peroxide is below 3.0 weight portions, obtained by resin combination when sheetmolding is extruded To solar cell sealing piece do not produce gel, the torque of extruder, sheetmolding can be suppressed to become easy.Piece also due to Jello is not produced in extruder, therefore the surface of piece does not have concavo-convex, outward appearance is good.Further, since without gel, even if therefore , there is no the cracking that the jello inside by piece causes in applied voltage, therefore insulation breakdown resistance is good yet.Additionally, poisture-penetrability Also it is good.Further, since there is no concavo-convex on piece surface, thus it is transparent with face side in the lamination process of solar module Protection component, unit, electrode, rear side protect the cementability of component also good.
(UV absorbent)
The solar cell sealing material of present embodiment is inhaled comprising the enumerate BTA system ultraviolet shown in formula (1) or (2) Receive agent.The light deterioration of enumerate BTA system UV absorbent is few, with excellent durability.Additionally, the ripple with below 300nm Absorbability under long, and there is maximum level wavelength in more than 340nm, it is excellent in the ultraviolet absorption ability of wide wavelength region It is different, and ultraviolet absorption ability can be for a long time maintained, the reduction of the conversion efficiency of solar module can be suppressed.
(in formula, R1Represent the alkyl of hydrogen atom or carbon number 1～6, R2～R4Can be the same or different, represent The alkyl oxygen of hydrogen atom, the alkyl of carbon number 1～20, hydroxyl, the alkoxyl of carbon number 1～22 or carbon number 1～22 Base carbonyl.)
(in formula, R1Represent the alkyl of hydrogen atom or carbon number 1～6, R5～R8Can be the same or different, represent The alkyl oxygen of hydrogen atom, the alkyl of carbon number 1～20, hydroxyl, the alkoxyl of carbon number 1～22 or carbon number 1～22 Base carbonyl.)
Above-mentioned formula (1) and the R of (2)1As long as in the alkyl straight-chain of carbon number 1～6 or the alkyl of branched be Can.As abovementioned alkyl, specifically, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth can be enumerated Base, sec-butyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl and n-hexyl etc..
As above-mentioned formula (1) and the R of (2)2～R4Or R5～R8In carbon number 1～20 alkyl, first can be enumerated Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, n-pentyl, isopentyl, neopentyl, uncle penta Base, n-hexyl, nonyl, decyl, dodecyl, undecyl, tridecyl, myristyl, pentadecyl, cetyl, ten Seven alkyl, octadecyl, nonadecyl and eicosyl etc..
Above-mentioned formula (1) and the R of (2)2～R4Or R5～R8As long as in carbon number 1～22 alkoxyl straight-chain or The alkoxyl of branched.Specifically, methoxyl group, ethyoxyl, isopropoxy, n-butoxy, isobutoxy, secondary can be enumerated Butoxy, tert-butoxy, positive hexyloxy and n-octyloxy etc..
Above-mentioned formula (1) and the R of (2)2～R4Or R5～R8In carbon number 1～22 alkyloxycarbonyl, as long as alkane The carbon number of base section is 1～22, straight-chain or branched alkyloxycarbonyl.Specifically, first can be enumerated Epoxide carbonyl, ethoxy carbonyl, isopropoxy carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl, tertiary fourth Epoxide carbonyl, positive hexyloxy carbonyl and n-octyloxy carbonyl etc..
In above-mentioned formula (1), R1Represent hydrogen atom, R2～R4Can be the same or different, but can preferably enumerate carbon number 1～10 alkyl.
As the enumerate BTA system UV absorbent shown in above-mentioned formula (1), specifically, can enumerate 2- (2H-1,2,3- Benzotriazole -2- bases) -4,6- DI-tert-butylphenol compounds, 2- (the chloro- 2H-1,2,3- benzotriazole -2- bases of 5-) -4,6- di-t-butyls Phenol, 2- (2H-1,2,3- benzotriazole -2- bases) -4,6- di-tert-pentyl phenols, 2- (the chloro- 2H-1,2,3- benzotriazole -2- of 5- Base) -4,6- di-tert-pentyl phenols, 2- (2H-1,2,3- benzotriazole -2- bases) -4-TBP, 2- (the chloro- 2H-1,2 of 5-, 3- benzotriazole -2- bases) -4-TBP, 2- (2H-1,2,3- benzotriazole -2- bases) -4- methylphenols, (5- is chloro- for 2- 2H-1,2,3- benzotriazole -2- bases) -4- methylphenols, 2- (2H-1,2,3- benzotriazole -2- bases) -6- dodecyl -4- first Base phenol, 2- (the chloro- 2H-1,2,3- benzotriazole -2- bases of 5-) -6- dodecyl -4- methylphenols, 2- (2H-1,2,3- benzos Triazole -2- bases) -4- methyl-6-tert-butylphenols, 2- (the chloro- 2H-1,2,3- benzotriazole -2- bases of 5-) -4- methyl-6-tert-butyls Base phenol, 2- (2H-1,2,3- benzotriazole -2- bases)-paracresol, 2- (the chloro- 2H-1,2,3- benzotriazole -2- bases of 5-)-to first Phenol, 2- (2H-1,2,3- benzotriazole -2- bases) -4,6- double (1- methyl isophthalic acids-phenylethyl) phenol, 2- (the chloro- 2H-1,2,3- of 5- Benzotriazole -2- bases) -4,6- double (1- methyl isophthalic acids-phenylethyl) phenol, 2- (2,4- dihydroxy phenyls) -2H-1,2,3- benzos Triazole, 2- (2H-1,2,3- benzotriazole -2- bases) -4- tert-octyl phenols, 2- (2H-1,2,3- benzotriazole -2- bases) -6- uncles Butyl -4- methylphenols, 2- (2H-1,2,3- benzotriazole -2- bases) -4- methyl-6-tert amyl phenols, 2- (2H-1,2,3- benzene And triazole -2- bases) -4- methyl-6-tert octyl phenols, 2- (2H-1,2,3- benzotriazole -2- the bases) -4- tert-butyl group -6- methylbenzene Phenol, 2- (2H-1,2,3- benzotriazole -2- bases) -6- methyl -4- tert-amyl phenols, 2- (2H-1,2,3- benzotriazole -2- bases) - 6- methyl -4- tert-octyl phenols, 2- (2H-1,2,3- benzotriazole -2- bases) -4- dodecyl -6- methylphenols, 2- (2H-1, 2,3- benzotriazole -2- bases) -5- thanatols, 2- (2H-1,2,3- benzotriazole -2- bases) -5- butoxy phenol, 2- (2H-1,2,3- benzotriazole -2- bases) -5- octyl group epoxide phenol, 2- (2H-1,2,3- benzotriazole -2- bases) -5- benzoxies Base phenol, 2- (2H-1,2,3- benzotriazole -2- bases) -4- methyl -6- (3,4,5,6- tetrahydrochysene phthalimido methyl) benzene Phenol, 2- (4- acryloxy -2- hydroxy phenyls) -2H-1,2,3- benzotriazole, 2- (4- pi-allyl epoxide -2- hydroxy phenyls) - 2H-1,2,3- benzotriazole etc..
In above-mentioned formula (2), preferred R1Represent hydrogen atom, R5With R8It is identical, R6With R7It is identical.
As the enumerate BTA system UV absorbent shown in above-mentioned formula (2), specifically, 2 can be enumerated, 2 '-methylene Double [6- (2H-1,2,3- benzotriazole -2- bases) -4- (1,1,3,3- tetramethyl butyls) phenol], 4,4 '-di-2-ethylhexylphosphine oxide [2- (2H-1,2,3- benzotriazole -2- bases) -5- thanatols], 4,4 '-di-2-ethylhexylphosphine oxide [2- (2H-1,2,3- benzotriazole -2- Base) -5- butoxy phenol], 4,4 '-di-2-ethylhexylphosphine oxide [2- (2H-1,2,3- benzotriazole -2- bases) -5- octyl group epoxide phenol] etc.. They can be used alone, it is also possible to which two or more is used in mixed way.
Wherein, as the enumerate BTA system UV absorbent shown in above-mentioned formula (1), preferably can enumerate 2- (2H-1,2,3- Benzotriazole -2- bases) -6- dodecyl -4- methylphenols and 2- (2H-1,2,3- benzotriazole -2- bases) tertiary pentyls of -4,6- two Phenol.
The content of the UV absorbent in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin The weight portion of copolymer 1 00 is preferably 0.05～5.0 weight portion, more preferably 0.1～4.5 weight portion.If UV absorbent Content within the above range, then the balancing good of weathering stability, crosslinking feature, therefore preferably.
(silane coupler)
Preferably further include olefinic unsaturated silane compound.Alkene in the solar cell sealing material of present embodiment The content of category unsaturated silane compound, relative to the weight portion of ethene-alpha-olefin copolymer 100, preferably 0.1～5 weight portion, More preferably 0.1～4 weight portion, particularly preferably 0.1～3 weight portion.
If the content of olefinic unsaturated silane compound is more than 0.1 weight portion, cementability is improved.On the other hand, If the content of olefinic unsaturated silane compound is below 5 weight portions, the Cost And Performance of solar cell sealing material Balance is good, furthermore, it is possible to suppress to be used to make olefinic unsaturated silane compound and second in the lamination of solar module The addition of the organic peroxide of alkene-alpha olefin copolymer graft reaction, is obtained when sheetmolding is extruded by resin combination Solar cell sealing piece become to be not likely to produce gel, therefore the rising of the torque of extruder can be suppressed, hold sheetmolding Easily.Further, since can suppress concavo-convex in the surface generation of piece because of the jello of generation in extruder, therefore can prevent The deterioration of outward appearance.Furthermore, it is possible to prevent applied voltage time slice inside from ftractureing, therefore the drop of breakdown voltage can be prevented It is low.In addition it is also possible to prevent the reduction of poisture-penetrability.Further, since can suppress concavo-convex in the generation of piece surface, therefore in solar energy Become with the adaptation of face side transparent protection member, unit, electrode, rear side protection component during the lamination process of battery module Well, cementability is also improved.
Olefinic unsaturated silane compound can use known compound, be not particularly limited.Specifically, Can using VTES, vinyltrimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-glycidoxypropyltrime,hoxysilane, γ aminopropyltriethoxy silane, γ-methacryloxypropyl three Methoxy silane etc..It is preferred that the good γ of cementability-glycidoxypropyl group methoxy silane, gamma-amino propyl group three can be enumerated Ethoxysilane, γ-methacryloxypropyl trimethoxy silane, VTES, 2- (3,4- epoxide rings Hexyl) ethyl trimethoxy silane, 3- glycidoxypropyl dimethoxysilanes, 3- glycidoxypropyl group trimethoxies Base silane, 3- glycidoxypropyl diethoxy silanes, 3- glycidoxypropyl group triethoxysilanes etc..It is preferred that can Enumerate the good 3- methacryloxypropyl trimethoxy silanes of cementability, 3- methacryloxypropyl triethoxies Silane, 3- acryloxypropyl trimethoxy silanes, VTES, 2- (3,4- epoxycyclohexyls) ethyl three Methoxy silane, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl diethoxy silanes.
(amine system of being obstructed light stabilizer)
The solar cell sealing material of present embodiment is preferably further comprising the amine system light stabilizer that is obstructed.Received by including Resistance amine system light stabilizer, can catch the free radical kind being harmful to ethene-alpha-olefin copolymer, suppress the product of new free radical It is raw.
As the amine system light stabilizer that is obstructed, it is possible to use double (2,2,6,6- tetramethyl -4- piperidyls) sebacates, poly- [{ 6- (1,1,3,3- tetramethyl butyls) amino -1,3,5- triazine -2,4- diyls } { (2,2,6,6- tetramethyl -4- piperidyls) is sub- Amino } hexa-methylene { (2,2,6,6- tetramethyl -4- piperidyls) imino group }] etc. amine system of being obstructed, hindered piperidine based compound etc..
In addition it is also possible to using the low molecular weight hindered amine system light stabilizer of following formulas (3).
In above-mentioned formula (3), R1、R2Represent hydrogen, alkyl etc..R1With R2Can be the same or different.R1And R2Preferably Hydrogen or methyl.R3Represent hydrogen, alkyl, alkenyl etc..R3Preferably hydrogen or methyl.
As the amine system light stabilizer that is obstructed shown in above-mentioned formula (3), specifically, 4- acryloxy -2 can be enumerated, 2,6,6- tetramethyl piperidines, 4- acryloxy -1,2,2,6,6- pentamethvls, 4- acryloxy -1- ethyl -2,2,6, 6- tetramethyl piperidines, 4- acryloxy -1- propyl group -2,2,6,6- tetramethyl piperidines, 4- acryloxy -1- butyl -2,2, 6,6- tetramethyl piperidines, 4- methacryloxy -2,2,6,6- tetramethyl piperidines, 4- methacryloxy -1,2,2,6, 6- pentamethvls, 4- methacryloxy -1- ethyl -2,2,6,6- tetramethyl piperidines, 4- methacryloxy -1- fourths Base-2,2,6,6- tetramethyl piperidines, 4- Fructus Crotonis acyloxy-2,2,6,6- tetramethyl piperidines, 4- crotonocyls Oxy-1-propyl group-2, 2,6,6- tetramethyl piperidines etc..
In addition it is also possible to be obstructed amine system light stabilizer using the high molecular shown in following formula.So-called high molecular is obstructed Amine system light stabilizer, refers to the amine system light stabilizer that is obstructed that molecular weight is 1000～5000.
The content of the amine system light stabilizer that is obstructed in the solar cell sealing material of present embodiment, relative to above-mentioned second The weight portion of alkene-alpha olefin copolymer 100, preferably 0.01～2.0 weight portion, more preferably 0.01～1.6 weight portion, it is especially excellent Elect 0.05～1.6 weight portion as.If the content of amine system of being obstructed light stabilizer is more than 0.01 weight portion, against weather and resistance to It is hot good.If the content of amine system of being obstructed light stabilizer is below 2.0 weight portions, can suppress to be produced by organic peroxide The annihilation of raw free radical, cementability, thermostability, crosslinking feature are good.
(hindered phenol series stabilizer)
The solar cell sealing material of present embodiment preferably further includes hindered phenol series stabilizer.It is obstructed by including Phenol system stabilizer, can in the presence of oxygen catch the free radical kind being harmful to ethene-alpha-olefin copolymer, suppress new free radical Generation, oxidative degradation can be prevented.
As hindered phenol series stabilizer, it is possible to use known compound, can enumerate for example, 1,1,3- tri--(2- Methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 2,2- thiobiss (4- methyl-6-tert-butylphenols), 7- octadecyl -3- (4 '-hydroxyl -3 ', 5 '-di-tert-butyl-phenyl) propionic ester, four-it is [sub- Methyl -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionate methane, the [3- (3,5- di-t-butyl -4- of tetramethylolmethane-four Hydroxy phenyl) propionic ester], triethylene glycol-bis- [3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) propionic ester], 1,6- oneself two Double (the just pungent sulfenyl) -6- (uncles of 4- hydroxyls -3,5- two of alcohol-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], 2,4- Butyl benzene amido) -1,3,5- triazines, three-(3,5- di-tert-butyl-4-hydroxyl benzyls)-isocyanuric acid esters, 2,2- be thio-two sub- Ethyl double [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], N, N '-hexamethylene bis (3,5- di-t-butyl -4- hydroxyls Base)-hydrocinnamamide, 2,4- double [(pungent sulfenyl) methyl]-orthoresol, 3,5- di-tert-butyl-4-hydroxyl benzyls-phosphonate ester-diethyl Base ester, four [methylene (3,5- di-t-butyl -4- hydroxy hydrocinnamates)] methane, octadecyl -3- (the tertiary fourths of 3,5- bis- Base -4- hydroxy phenyls) propionic ester, double [2- { 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) the propionyloxy } -1,1- two of 3,9- Methylethyl] oxaspiro [5.5] hendecanes of -2,4,8,10- four etc..Wherein, the particularly preferably [3- (3,5- bis- of tetramethylolmethane-four Tert-butyl-hydroxy phenyl) propionic ester], octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester.
The content of the hindered phenol series stabilizer in the solar cell sealing material of present embodiment, relative to ethylene-α-alkene The weight portion of hydrocarbon copolymer 100, preferably 0.005～0.1 weight portion, more preferably 0.01～0.1 weight portion, particularly preferably 0.01～0.06 weight portion.If the content of hindered phenol series stabilizer is more than 0.005 weight portion, thermostability is good, in example In the heat-proof aging test at a high temperature of more than 120 DEG C, there is the xanthochromia that can suppress solar cell sealing material.Such as The content of fruit hindered phenol series stabilizer is that below 0.1 weight portion, then the crosslinking feature of solar cell sealing material is good, heat-resisting Property, cementability are good.
Additionally, under constant temperature and humidity, if be used in combination with the amine system light stabilizer that is obstructed with alkalescence, hindered phenol stabilizer Hydroxyl forming salt, form the double quinone methides of conjugation of quinone and dimerization, have and be easy to cause solar cell sealing material Xanthochromia tendency, but if hindered phenol series stabilizer be 0.1 weight portion below, then can suppress solar cell sealing material Xanthochromia.
(phosphorus system stabilizer)
The solar cell sealing material of present embodiment preferably further includes phosphorus system stabilizer.If stable comprising phosphorus system Agent, the then decomposition of organic peroxide when can suppress extrusion molding, it is possible to obtain the good piece of outward appearance.If comprising being obstructed Amine system light stabilizer, hindered phenol series stabilizer, then can also fall into oblivion the free radical of generation, produce the good piece of outward appearance, but in piece Stabilizer is consumed in extrusion operation, there is the reduction of the long-term reliabilities such as thermostability, against weather.
As phosphorus system stabilizer, it is possible to use known compound, can enumerate for example, three (2,4- di-tert-butyls Base) phosphite ester, double [2,4- double (1,1- dimethyl ethyls) -6- aminomethyl phenyls] ethyl ester phosphorous acid, four (2,4- di-t-butyls Phenyl) [1,1- xenyls] -4,4 '-diyl biphosphinate and double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites Deng.Wherein, preferably three (2,4- di-tert-butyl-phenyl) phosphite ester.
The content of the phosphorus system stabilizer in the solar cell sealing material of present embodiment, it is common relative to ethene-alpha-olefin The weight portion of polymers 100, preferably 0.005～0.5 weight portion, more preferably 0.01～0.5 weight portion, particularly preferably 0.02～ 0.2 weight portion.If the content of phosphorus system stabilizer is more than 0.005 weight portion, organic mistake during extrusion molding can be suppressed The decomposition of oxide, it is possible to obtain the good piece of outward appearance.Additionally, thermostability is good, it is resistance at a high temperature of such as more than 120 DEG C In thermal aging test, there is the xanthochromia that can suppress solar cell sealing material.If the content of phosphorus system stabilizer is 0.5 Below weight portion, then the crosslinking feature of solar cell sealing material is good, and thermostability, cementability are good.Additionally, having no by phosphorus system , there is no metal erosion in the impact that the acid band that the decomposition of stabilizer is produced is come yet.
In addition, though have same intramolecular that there is the stabilizer of phosphite ester structure and hindered phenol structure, but such as this enforcement In the such compositionss containing organic peroxide in large quantities of the solar cell sealing material of mode, suppress during extrusion molding organic The performance of the decomposition of peroxide is insufficient, has the tendency of to generate gel and cannot get the good piece of outward appearance.
(other additives)
In the resin combination of the solar cell sealing material for constituting present embodiment, in the model for not damaging the object of the invention In enclosing, can suitably containing the various composition beyond each composition described in detail above.Can enumerate for example, ethene-alpha-olefin copolymer Various polyolefin in addition；Polystyrene, ethylene based block copolymer；Acrylic polymer etc..In solar cell sealing material Various composition content, relative to the weight portion of above-mentioned ethene-alpha-olefin copolymer 100, preferably 0.0001～50 weight Part, more preferably 0.001～40 weight portion.In addition it is also possible to it is appropriate containing selected from various resins in addition to the polyolefin, And/or various rubber, plasticizer, filler, pigment, dyestuff, antistatic additive, antibacterial, antifungus agent, fire retardant, crosslinking coagent, One or more of other heat-resisting stabilizing agents and dispersant in addition to hindered phenol series stabilizer and phosphorus system stabilizer etc. Additive.
As other heat-resisting stabilizing agents in addition to hindered phenol series stabilizer and phosphorus system stabilizer, specifically, can be with Enumerate the lactone system heat-resisting stabilizing agents such as the reaction product of 3- hydroxyls -5,7- di-t-butyls-furan -2- ketone and o-Dimethylbenzene；Two Myristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate, two-tridecyl sulfur For dipropionate, tetramethylolmethane-four-(β-lauryl-thiopropionate), 2-mercaptobenzimidazole, 2-mercaptobenzimidazole Zinc salt, 2 mercaptomethyl benzimidazole, the zinc salt of 2 mercaptomethyl benzimidazole, 4,4 '-thiobiss (the 6- tert-butyl group -3- methyl Phenol), the sulfur system Heat-resistant stable such as 2,6- di-t-butyl -4- (4,6- double (pungent sulfenyl) -1,3,5- triazine -2- base amino) phenol Agent；Amine system heat-resisting stabilizing agent etc..
Particularly, in the case of containing crosslinking coagent, the crosslinking in the solar cell sealing material of present embodiment is helped The content of agent, relative to the weight portion of ethene-alpha-olefin copolymer 100, preferably 0.05～5 weight portion, more preferably 0.1～3 Weight portion.If the content of crosslinking coagent is within the above range, there can be the cross-linked structure of appropriateness, can improve heat-resisting Property, mechanical properties, cementability, therefore preferably.
As crosslinking coagent, it is possible to use for the known crosslinking coagent that olefin-based resin is usually used.So Crosslinking coagent be intramolecular have more than one double bond compound.Specifically, tert-butyl acrylate, acrylic acid can be enumerated Lauryl Ester, acrylic acid spermaceti base ester, stearyl acrylate base ester, 2- methoxyethyl acrylates, ethyl carbitol acrylic acid The mono acrylic esters such as ester, methoxyl group tripropylene glycol acrylate；Tert-butyl Methacrylate, lauryl methacrylate, first Base acrylic acid spermaceti base ester, stearyl methacrylate, methoxyl group glycolmethacrylate, methoxy poly (ethylene glycol) first The monomethacrylates such as base acrylate；1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, 1,9- nonyls two Alcohol diacrylate, neopentylglycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, poly- second two The diacrylates such as alcohol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate；1,3 butylene glycol diformazan Base acrylate, 1,6-HD dimethylacrylate, 1,9- nonanediol dimethylacrylates, neopentyl glycol dimethyl propylene It is olefin(e) acid ester, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, poly- The dimethylacrylates such as ethylene glycol dimethacrylate；Trimethylolpropane trimethacrylate, tetramethylol methane 3 third The triacrylates such as olefin(e) acid ester, pentaerythritol triacrylate；Trimethylol-propane trimethacrylate, trimethylolethane The trimethyl acrylic esters such as trimethyl acrylic ester；Tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate etc. four Acrylate；The di vinyl aromatic compounds of group such as divinylbenzene, di isopropenylbenzene；Triallylcyanurate, triolefin The cyanurates such as propyl group isocyanuric acid ester；The diallyl compounds such as diallyl phthalate；Triallyl compound； The oximes such as paraquinonedioxime, p, p '-dibenzoyl quininie dioxime；The maleimides such as phenyl maleimide.
Diacrylate is more preferably in these crosslinking coagents；Dimethylacrylate；Di vinyl aromatic race chemical combination Thing；Three acrylic acid such as trimethylolpropane trimethacrylate, tetramethylol methane triacrylate, pentaerythritol triacrylate Ester；The trimethyl acrylic esters such as trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate；Season penta The tetraacrylates such as tetra-acrylate, tetramethylol methane tetraacrylate；Triallylcyanurate, triallyl are different The cyanurates such as cyanurate；The diallyl compounds such as diallyl phthalate；Triallyl compound；Paraquinones two The oximes such as oxime, p, p '-dibenzoyl quininie dioxime；The maleimides such as phenyl maleimide.Additionally, in these crosslinking coagents especially Preferably Triallyl isocyanurate, the bubble of the solar cell sealing material after lamination occurs, the balance of crosslinking feature It is most excellent.
The solar cell sealing material of present embodiment, by relative to the above-mentioned weight of ethene-alpha-olefin copolymer 100 Part, the content of UV absorbent is 0.05～5.0 weight portion, and the content of organic peroxide is 0.1～3 weight portion, is obstructed The content of phenol system stabilizer is 0.005～0.1 weight portion, and the content of amine system of being obstructed light stabilizer is 0.01～2.0 weight portion, phosphorus It is optimal way that the content for being stabilizer is the resin combination formation of 0.005～0.5 weight portion.
Additionally, the solar cell sealing material of present embodiment, by relative to above-mentioned ethene-alpha-olefin copolymer 100 Weight portion, the content of UV absorbent is 0.1～4.5 weight portion, and the content of organic peroxide is 0.2～2.5 weight portion, The content of hindered phenol series stabilizer is 0.01～0.06 weight portion, and the content of amine system of being obstructed light stabilizer is 0.05～1.6 weight Part, it is particularly preferred mode that the content of phosphorus system stabilizer is that the resin combination of 0.02～0.2 weight portion formed.
The solar cell sealing material of present embodiment, against weather is excellent, and with face side transparent protection member, the back of the body Surface side protection component, membrane electrode, aluminum, the cementability of the various solaode components such as solar cell device, thermostability, The balance of extrusion molding and crosslinking feature, the transparency, flexibility, outward appearance, electrical characteristic, electrical insulating property, poisture-penetrability, electrode are rotten The balancing good of corrosion, technology stability.Therefore, the solaode for being suitable as known solar module is close Seal material and use.Can by the use of commonly used approach as the manufacture method of the solar cell sealing material of present embodiment, But it is preferred that carry out melt blending to manufacture by kneader, Banbury mixer, extruder etc..Particularly preferably passing through can be continuous The extruder of production is manufacturing.
Solar cell sealing material, its global shape is also one of preferred embodiment for lamellar.Additionally, having at least One layer of piece comprising above-mentioned resin combination simultaneously can also be adapted to solar cell sealing material obtained by other layer of Composite Use.The thickness of the layer of solar cell sealing material is usually 0.01～2mm, preferably 0.05～1.5mm, more preferably 0.1 ～1.2mm, more preferably 0.2～1mm, particularly preferably 0.3～0.9mm, most preferably 0.3～0.8mm.If thickness Within the range, then face side transparent protection member, solar cell device, membrane electrode etc. in lamination can be suppressed Breakage, also, by assuring that sufficient light transmittance, it is hereby achieved that high light generated energy.Furthermore, it is possible to carry out low temperature Under solar module it is laminated into type, therefore preferably.
The forming method of solar cell sealing material piece is not particularly limited, but can adopt known various forming methods (cast molding, extrusion sheetmolding, inflation molding, injection moulding, compression forming, calendering formation etc.).Particularly, in extruder In, by UV absorbent, organic peroxide, the silane coupler and according to need of ethene-alpha-olefin copolymer and the present invention The amine system light stabilizer that is obstructed, hindered phenol series stabilizer, phosphorus system stabilizer, crosslinking coagent and other additives wanted are for example in modeling After manpower blending is carried out in the bags such as pocket, being blended using stirring mixers such as Henschel mixer, rotating cylinder, high-speed mixers , be combined with ethene-alpha-olefin copolymer and the resin combination of various additives put into extrusion sheetmolding hopper in, enter Row melting mixing, while carrying out extrusion sheetmolding, the solar cell sealing material for obtaining lamellar is most preferred embodiment.
In addition, once pelletized using extruder with the resin combination with synthesis, and then by extrusion molding, compacting When molding carries out piece, it is however generally that pass through from water layer, or using imderwater cutting machine formula extruder cool down strands, cutting and Obtain granule.Therefore, because attachment of moisture, therefore there is the deterioration that additive is particularly silane coupler, for example use again and squeeze When going out machine and carrying out piece, the mutual condensation reaction of silane coupler is carried out, and has the tendency of cementability reduction, therefore not preferred.This Outward, by ethene-alpha-olefin copolymer, (hindered phenol series are stable with the additive in addition to organic peroxide, silane coupler The stabilizers such as agent, phosphorus system stabilizer, amine system of being obstructed light stabilizer, UV absorbent) in advance using after extruder masterbatch, mix Mixed organic peroxide, silane coupler, in the case of carrying out sheetmolding with extruder etc. again, also due to hindered phenol series are stable Two degree of the stabilizers such as agent, phosphorus system stabilizer, amine system of being obstructed light stabilizer, UV absorbent have stable by extruder Agent is deteriorated, the tendency that the long-term reliability such as against weather, thermostability is reduced, therefore not preferred.
Used as extrusion temperature scope, extrusion temperature is 100～130 DEG C.If making extrusion temperature for more than 100 DEG C, can So that the productivity of solar cell sealing material is improved.If making extrusion temperature for less than 130 DEG C, resin combination is used and is squeezed Become to be not susceptible to gelation when going out Bigpian and obtaining solar cell sealing material.Accordingly it is possible to prevent the torque of extruder Rising, make sheetmolding easy.Further, since becoming to be not likely to produce on the surface of piece concavo-convex, therefore deteriorated appearance can be prevented. Furthermore, it is possible to suppress to be ftractureed inside applied voltage time slice, therefore the reduction of breakdown voltage can be prevented.Additionally, The reduction of poisture-penetrability can also be suppressed.Further, since become to be not likely to produce on piece surface it is concavo-convex, therefore in solar module Lamination process when with face side transparent protection member, unit, electrode, rear side protection component adaptation become good, glue Connecing property is excellent.
Additionally, in the case where the MFR of ethene-alpha-olefin copolymer is for e.g., less than 10g/10 minutes, use is by inciting somebody to action Molten resin warmed-up metallic roll (stack) is rolled so as to make the calendering formation machine of the piece of desired thickness, film, Carrying out ethene-alpha-olefin copolymer and silane coupler, organic peroxide, UV absorbent, light stabilizer, heat-resisting steady Calendering formation is carried out while the melting mixing for determining agent and other additives for using as needed, it is also possible to obtain lamellar is too Positive energy cell sealing material.
As calendering formation machine, it is possible to use known various calendering formation machines, it is possible to use mixing mill, three-roller calendaring Machine, four-roll calender.As four-roll calender, especially can be using I types, S types, inverted L shape, Z-type, oblique Z-type etc..Additionally, It is preferred that before stack is imposed on, in advance vinylite compositionss are heated to into appropriate temperature, for example, it is close that Banbury is set Mill, kneader, extruder etc. are also one of preferred embodiment.The temperature range of calendering formation is preferably leads to roll temperature It is often 40～100 DEG C.
Furthermore, it is possible to implement Embossing processing to the surface of the piece (or layer) of solar cell sealing material.By Embossing processing To decorate the piece surface of solar cell sealing material such that it is able to prevent sealing material piece each other or sealing material piece and other pieces etc. Adhesion.Further, since the storage elastic modulus of solar cell sealing material (solar cell sealing material piece) drops in embossing It is low, therefore solar cell sealing material piece and solar cell device are being become to the slow of solar cell device etc. when being laminated Punching, such that it is able to prevent the breakage of solar cell device.
Total volume V of the recess of the per unit area of the piece of solar cell sealing materialHWith solar cell sealing material Piece apparent volume VAPercentage ratio (VH/VAVoidage P (%) shown in) × 100 is preferably 10～50%, more preferably 10 ～40%, more preferably 15～40%.In addition, the apparent volume V of the piece of solar cell sealing materialABy by unit plane Product is multiplied by the maximum gauge of solar cell sealing material and obtains.If voidage P is more than 10%, solar-electricity can be made The elastic modelling quantity of pond sealing material is fully reduced, therefore can obtain sufficient resiliency.Therefore, in the manufacturing process of module, When carrying out lamination process (pressurization operation) with the two-stage, for crystal type solaode, can prevent silicon unit, silicon The cracking of the solder that unit is fixed with electrode, for thin film solar cell, can prevent the cracking of silver electrode. That is, if the voidage of the solar cell sealing material comprising the piece formed by resin combination is more than 10%, even if In the case of being partly applied with pressure to solar cell sealing material, be applied with the convex portion of pressure also can be become in the way of shriveling Shape.Therefore, in lamination process, even if being for example partly applied with big pressure to silicon unit etc., it is also possible to prevent silicon unit Cracking.Additionally, if the voidage of solar cell sealing material is more than 10%, may insure the passage of air, therefore Can deaerate well during lamination process.Accordingly it is possible to prevent in solar module residual air and deteriorated appearance, or There is the corrosion of electrode due to the moisture in the air of residual in life-time service.Additionally, in lamination, the resin group of flowing Space produced by compound tails off, therefore can prevent from being exuded to the outside of each adherend of solar module and pollution layer Press.
On the other hand, if voidage P is less than 80%, air can take off well in the pressurization of lamination process Gas, therefore the residual air in solar module can be prevented.It is therefore possible to prevent the evil of the outward appearance of solar module Change, also the corrosion of electrode will not occur due to the moisture in the air of residual in life-time service.Additionally, air adds in lamination Can deaerate well during the pressurization of work, therefore solar cell sealing material increases with the bond area of adherend, it is possible to obtain Sufficient adhesive strength.
Voidage P can be obtained by calculating as following.Implement the solar cell sealing material of Embossing processing Apparent volume VA(mm3) by the maximum gauge t of solar cell sealing materialmax(mm) with unit area (such as 1m2= 1000mm × 1000mm=106mm2) product, calculate as following formula (12).
VA(mm3)=tmax(mm)×106(mm2) (12)
On the other hand, the actual volume V of the solar cell sealing material of the unit area0(mm3) by the way that solar energy will be constituted Proportion ρ (the g/mm of the resin of cell sealing material3) and per unit area (1m2) solar cell sealing material actual weight W G () substitutes into following formula (13) to calculate.
V0(mm3)=W/ ρ (13)
Total volume V of the recess of the per unit area of solar cell sealing materialH(mm3), such as shown in following formula (14), By from " the apparent volume V of solar cell sealing materialA" in deduct " actual volume V0" calculating.
VH(mm3)=VA-V0=VA-(W/ρ) (14)
Therefore, voidage P (%) can be obtained as follows.
Voidage P (%)=(VH/VA)×100
=((VA-(W/ρ))/VA)×100
=(1-W/ (ρ VA))×100
=(1-W/ (ρ tmax·106))×100
Voidage P (%) can be obtained by above-mentioned calculating formula, but it is also possible to by actual solaode The section of sealing material, the face for implementing Embossing processing carry out microscope photographing, and carry out image procossing etc. obtaining.
The depth of the recess formed by Embossing processing be preferably the maximum gauge of solar cell sealing material 20～ 95%, more preferably 50～95%, more preferably 65～95%.Sometimes by depth D of recess relative to piece maximum gauge tmax Percentage ratio be referred to as " the depth rate " of recess.
The depth of the recess of so-called Embossing processing, represents the male and fomale(M＆F) of the solar cell sealing material obtained by Embossing processing , the difference of height D in the most deep of the top of convex portion and recess.Additionally, the maximum gauge of so-called solar cell sealing material tmax, in the case where a face to solar cell sealing material carries out Embossing processing, represent the most top from the convex portion in a face Portion to another face (solar cell sealing material thickness direction) distance, in two face realities to solar cell sealing material In the case of having applied Embossing processing, represent from the top of the convex portion in a face to the top of the convex portion in another face (too Positive energy cell sealing material thickness direction) distance.
Embossing processing can be implemented to the one side of solar cell sealing material, it is also possible to which two sides is implemented.In increase embossing In the case of the depth of the recess of processing, preferably only formed in the one side of solar cell sealing material.Only to solaode In the case that the one side of sealing material implements Embossing processing, the maximum gauge t of solar cell sealing materialmaxFor 0.01mm～2mm, Preferably 0.05～1mm, more preferably 0.1～1mm, more preferably 0.15～1mm, more preferably 0.2～1mm, More preferably 0.2～0.9mm, particularly preferably 0.3～0.9mm, most preferably 0.3～0.8mm.If solaode The maximum gauge t of sealing materialmaxWithin the range, then face side transparent protection member, solar-electricity in lamination can be suppressed The breakage of pond element, membrane electrode etc., even if the laminated into type of solar module can also be carried out than relatively low temperature, Therefore preferably.Additionally, solar cell sealing material may insure sufficient light transmittance, the solar cell sealing has been used The solar module of material has high light generated energy.
Additionally, the piece can be in the lobule form that cut into according to solar module size or can be will Make and solar cell sealing material is used as according to the roll form that size cuts before solar module.As present embodiment The solar cell sealing material (solar cell sealing material piece) of the lamellar of preferred implementation is as long as have at least one of which by too The layer that positive energy cell sealing material is formed.Therefore, the number of plies of the layer for being formed by the solar cell sealing material of present embodiment Can be one layer, or more than two layers.From the viewpoint for making simple structure and reduces cost, and the interface for strongly reducing interlayer Reflect and effectively utilize the consideration such as viewpoint of light, preferably one layer.
Solar cell sealing material piece, the layer that only can be formed by the solar cell sealing material of present embodiment is constituted, There can also be the layer (hereinafter, also referred to as " other layers ") beyond the layer containing solar cell sealing material.As other layers Example, if classified according to purpose, can enumerate hard conating, adhesive linkage, anti-reflection layer, the resistance for surface or back-protective Gas-bearing formation, stain-proofing layer etc..If classified according to material, can enumerate formed by uv curing resin layer, by thermosetting The layer of resin formation, the layer formed by vistanex, the layer formed by carboxyl acid modified vistanex, formed by fluorine resin Layer, the layer formed by cyclic olefin (co) polymer, the layer that formed by inorganic compound etc..
The layer formed by the solar cell sealing material of present embodiment is not particularly limited with the position relationship of other layers, Preferred layer is suitably selected to constitute according to the relation with the purpose of the present invention.That is, other layers can be arranged on more than 2 layers by too Between the layer that positive energy cell sealing material is formed, it is also possible to be arranged on the outermost layer of solar cell sealing material piece, can also arrange Where in addition.Furthermore, it is possible to only other layers are set in the one side of the layer formed by solar cell sealing material, Other layers can be set on two sides.The number of plies of other layers is not particularly limited, and can arrange other layers of the arbitrary number of plies, also may be used To be not provided with other layers.
From the viewpoint for making simple structure and reduces cost, and strongly reduce interface reflection and effectively utilize viewpoint of light etc. Consider, be not provided with other layers and only close with the layer making solaode formed by the solar cell sealing material of present embodiment Envelope material piece.If however, there are other necessary or useful layers according to the relation with purpose, as long as being appropriately arranged with that Other layers of sample.For the layer formed by the solar cell sealing material of present embodiment arranged in the case of other layers With the laminating method of other layers, it is not particularly limited, but preferably with cast molding machine, extrusion panel forming machine, inflation molding The method that melt extruder known to machine, injection (mo(u)lding) machine etc. is coextruded and obtains laminated body, or at one layer of advance comprising Upper melting or another layer of heated lamination and the method that obtains laminated body.Furthermore, it is possible to by using appropriate bonding agent (example Such as, (trade name " ADOMER (registered trade mark) " of Mitsui Chemicals, Inc.'s system, Mitsubishi Chemical are public for maleic anhydride modified vistanex Trade name " MODIC (registered trade mark) " etc. of department's system), low (non-) the crystallinity soft polymer such as unsaturated polyolefin, with ethylene/ Acrylate/maleic anhydride terpolymer (trade name " Bondine (registered trade mark) " of Zhu Hua CdF chemical companies etc.) is The acrylic acid series bonding agent of representative, Ethylene/vinyl acetate based copolymer or the adhesive resin compositionss comprising them etc.) Dry lamination method or lamination methods etc. carry out lamination.As bonding agent, the thermostability with 120～150 DEG C or so is preferably used Bonding agent, Polyester or urethane adhesive etc. can be illustrated as suitable bonding agent.Additionally, in order to improve two-layer Cementability, it is, for example possible to use silane system coupling processing, titanium system coupling processing, sided corona treatment, corona treatment etc..
2. with regard to solar module
Solar module, can enumerate for example, generally will be used by the solar cell device of the formation such as polycrystal silicon Solar cell sealing material piece is clamped and lamination, and then the crystal type solaode mould that the exterior and the interior two sides is covered with screening glass Block.That is, typical solar module is solar module screening glass (face side transparent protection member)/solar energy Cell sealing material/solar cell device/solar cell sealing material/solar module screening glass (protect by rear side Component) such composition.However, as the solar module one of preferred embodiment of present embodiment, not limiting Due to above-mentioned composition, do not damaging in the range of the purpose of the present invention, can suitably omit a part for above-mentioned each layer, or Person is appropriately arranged with layer other than the above.As layer other than the above, can enumerate for example adhesive linkage, impact absorbing layer, coating layer, Anti-reflection layer, the back side reflecting layer and light diffusion layer etc. again.These layers are not particularly limited, but can consider to arrange the mesh of each layer , characteristic and arrange in position.
(solar module of crystalline silicon)
Fig. 1 is the sectional view of an embodiment of the solar module for schematically showing the present invention.In addition, in Fig. 1 In, one of the composition of the solar module 20 of display crystalline silicon.As shown in figure 1, solar module 20 has The solar cell device 22 of the multiple crystalline silicons electrically connected by interconnector 29, clamp the solaode A pair of face side transparent protection members 24 of element 22 and rear side protection component 26, in these protection components and multiple solar energys Sealant 28 is filled between cell device 22.Sealant 28 is by making the sealing material used for solar batteries of present embodiment After laminating, plus it is thermally compressed and obtains, connects with the electrode of the sensitive surface and the back side that are formed at solar cell device 22.So-called electricity Pole is the sensitive surface and the collector component that formed respectively of the back side in solar cell device 22, comprising collection electric wire described later, attached pole Ear bus and back electrode layer etc..
Fig. 2 is the plane graph of a configuration example at the sensitive surface and back side for schematically showing solar cell device.In Fig. 2 In, one of the composition of the sensitive surface 22A and back side 22B of display solar cell device 22.As shown in Fig. 2 (A), in solar energy The sensitive surface 22A of cell device 22, be formed with a plurality of collection electric wire 32 for being formed as wire and from collection electric wire 32 collect electric charge and with Attached lug bus (busbar) 34A of interconnector 29 (Fig. 1) connection.Additionally, as shown in Fig. 2 (B), in solaode unit The back side 22B of part 22, whole face is formed with conductive layer (backplate) 36, be formed on from conductive layer 36 collect electric charge and with Attached lug bus (busbar) 34B of interconnector 29 (Fig. 1) connection.The live width of collection electric wire 32 is such as 0.1mm or so；It is attached The live width of lug bus 34A is such as 2～3mm or so；The live width of attached lug bus 34B is such as 5～7mm or so.Collection The thickness of electric wire 32, attached lug bus 34A and attached lug bus 34B is such as 20～50 μm or so.
Collection electric wire 32, attached lug bus 34A and attached lug bus 34B preferably comprise the high metal of electric conductivity.So The high metal of electric conductivity example in comprising gold, silver, copper etc., but from electric conductivity, corrosion resistance it is high in terms of etc. consider, preferably For silver, silver compound, the alloy containing silver etc..Conductive layer 36 not only comprising the high metal of electric conductivity, and from making in sensitive surface Suffered light reflects and makes the photoelectric transformation efficiency of solar cell device improve the considerations such as such viewpoint, further preferably comprising light The high composition of reflexive, such as aluminum.Collection electric wire 32, attached lug bus 34A, attached lug bus 34B and conductive layer 36 pass through Solar cell device 22 sensitive surface 22A or back side 22B for example, by screen painting by comprising the high gold of above-mentioned electric conductivity The conduction material coatings of category are dried into after 50 μm of coating thickness, sinter to be formed at such as 600～700 DEG C as needed.
Face side transparent protection member 24 is due to being configured in light surface side, it is therefore desirable to for transparent.Face side is transparency protected In the example of component 24, comprising transparency glass plate, transparent resin film etc..On the other hand, rear side protection component 26 need not be Transparent, its material is not particularly limited.In the example of rear side protection component 26, comprising glass substrate, plastic foil etc., but from resistance to Long from the viewpoint of property, the transparency, it is adapted to use glass substrate.
Solar module 20 can be obtained by arbitrary manufacture method.Solar module 20, for example may be used To be obtained by following operations：Obtain by rear side protection component 26, solar cell sealing material, multiple solaodes unit The operation of part 22, solar cell sealing material and face side transparent protection member 24 laminated body of lamination successively；This is folded Layer body carries out pressurization by laminating machine etc. makes it fit, while the operation for heating as needed；After above-mentioned operation, Jin Ergen According to needing to carry out heat treated to laminated body, by the operation of above-mentioned sealing material solidification.
In solar cell device, it is commonly configured with for taking out the electric collecting electrodes for producing.The example of collecting electrodes In, comprising bus bar electrode, finger electrode etc..In general, collecting electrodes can be adopted is configured in solar cell device The structure on the two sides at surface and the back side, but if configuring collecting electrodes in sensitive surface, then because collecting electrodes cover light, therefore can Problem as decrease of power generation can be produced.
Additionally, in order that generating efficiency is improved, it is possible to use the back contacts type of collecting electrodes need not be configured in sensitive surface Solar cell device.In the form of back contacted solar cell element, in the sensitive surface of solar cell device Rear side set by opposition side, is arranged alternately p doped regions and n doped regions.In back contacted solar cell element In other forms, p/n engagements are formed in the substrate of through hole (through hole) is provided with, form the doped layer of surface (sensitive surface) side Until through-hole wall and the bore periphery portion of rear side, overleaf side draw goes out the electric current of sensitive surface.
In general, in solar cell system, by above-mentioned solar module number of concatenated connection platform to tens of Platform, even the small-scale system of house is being referred to as the extensive of large-sized solar generating also with 50V～500V utilizations System in 600～1000V utilization.For the housing of solar module, for the purpose of intensity holding etc. aluminum is used Framework etc., considers, the situation that aluminium chassis are grounded (earth) is more from viewpoint for security.As a result, passing through solar-electricity Pond generate electricity, between the face side transparent protection member face low with sealing material phase ratio resistance and solar cell device, produce by The voltage difference that generating causes.
As a result, for the solar energy being sealed between generator unit and face side transparent protection member or aluminium chassis Cell sealing material, it is desirable to the good electrical characteristic such as high electrical insulating property, high resistance.
(solar modules of thin film silicon systems (amorphous silicon systems))
The solar module of thin film silicon systems can be, (1) is by face side transparent protection member (glass substrate)/thin film The module of solar cell device/sealant/rear side protection component lamination successively；(2) by the transparency protected structure of face side Part/sealant/Thinfilm solar cell component/sealant/rear side protects component module of lamination etc. successively.Face side Transparent protection member, rear side protection component and sealant are same with the situation of above-mentioned " solar module of crystalline silicon " Sample.
(1) the Thinfilm solar cell component in form for example includes successively transparent electrode layer/pin types silicon layer/back side Electrode layer.In the example of transparent electrode layer, comprising In2O3、SnO2、ZnO、Cd2SnO4, ITO is (in In2O3In with the addition of Sn and obtain) Deng quasiconductor system oxide.Back electrode layer includes such as Ag films layer.Each layer passes through plasma CVD (chemical vapor deposition) Method, sputtering method and formed.Sealant is configured in the way of connecting with back electrode layer (such as Ag films layer).Due to transparency electrode Layer is formed on face side transparent protection member, therefore sealant is not often configured in face side transparent protection member with transparent electricity Between the layer of pole.
(2) Thinfilm solar cell component of form successively comprising such as transparent electrode layer/pin types silicon layer/metal forming, Or it is configured in the metal film layer on thermostability polymeric membrane (for example, Ag films layer).In the example of metal forming, comprising rustless steel Steel foil etc..In the example of thermostability polymeric membrane, comprising polyimide film etc..Transparent electrode layer and pin types silicon layer are same with above-mentioned Formed by CVD, sputtering method sample.That is, pin types silicon layer is formed at metal forming or configures on thermostability polymeric membrane Metal film layer；And then transparent electrode layer is formed at pin type silicon layers.Additionally, the metal being configured on thermostability polymeric membrane Thin layer also can be formed by CVD, sputtering method.
In this case, sealant is arranged respectively between transparent electrode layer and face side transparent protection member；And gold Between category paper tinsel or thermostability polymeric membrane and rear side protection component.So, the sealant for being obtained by solar cell sealing material The electrode of collection electric wire, attached lug bus and conductive layer with solar cell device etc. connects.Additionally, the form of (2) is thin Film solar cell element, because silicon layer is thinner than the solar cell device of crystalline silicon, therefore is difficult due to solaode It is damaged from outside impact when pressurization, above-mentioned module during modular manufacture works.Therefore, with the solar energy of crystalline silicon Comparing used by battery module, the flexibility of the solar cell sealing material used by film solar battery module can be low.Separately On the one hand, because the electrode of above-mentioned Thinfilm solar cell component is as described above metal film layer, therefore due to corruption Erosion and deteriorate in the case of, generating efficiency may be significantly reduced.
Additionally, as other solar modules, there is used in solar cell device the solaode of silicon Module.In the solar module of silicon used in solar cell device, can enumerate and fold silicon metal and amorphous silicon Mixed type (HIT types) solar module of layer, by many engagements of the different silicon layer lamination of absorbing wavelength region Type (tandem type) solar module, in the rear side set by the opposition side of the sensitive surface of solar cell device alternately It is provided with the back contacted solar cell module of p doped regions and n doped regions, (diameter 1mm is left by countless spherical silicon particles It is right) the spherical silicon type solaode mould that combines with the concave mirror (doubling as electrode) of the 2～3mm of diameter for improving light gathering Block etc..Additionally, in the solar module of silicon used in solar cell device, also can enumerate with by conventional tool The p-type window layer for playing the role of the amorphous silicon type of pin connected structures is replaced as " imitating by field by " transparency electrode for having been insulated " Field effect type solar module of structure of the inversion layer answered and induce " etc..Additionally, can enumerate in solar cell device Used in the GaAs systems solar module of the GaAs of monocrystalline；As solar cell device, replace silicon and used by The CIS or CIGS (Chalkopyrite of the I-III-VI group compound for being referred to as Chalkopyrite system of the compositions such as Cu, In, Ga, Al, Se, S System) solar module；Used Cd compound films as solar cell device CdTe-CdS systems solaode, Cu2ZnSnS4(CZTS) solar module etc..It is all too that the solar cell sealing material of present embodiment can serve as these The solar cell sealing material of positive energy battery module.Wherein it is possible to being suitable for lamination has the mixing of silicon metal and amorphous silicon Type (HIT types) solar module, lamination have many maqting types (tandem type) of the different silicon layer of absorbing wavelength region.
Particularly, the sealing material layer being stacked under the photovoltaic cell for constituting solar module, needs to have Sealing material layer, electrode, the cementability of back-protective layer with the top for being stacked in photovoltaic cell.Additionally, in order to keep making For the flatness at the back side of the solar cell device of photovoltaic cell, need with thermoplasticity.Additionally, in order to protect conduct The solar cell device of photovoltaic cell, needs marresistance, impact absorbency etc. excellent.
As above-mentioned sealing material layer, preferably with thermostability.Particularly preferably when solar module is manufactured, Bu Huiyou Sunlight in evacuation and when adding the life-time service of heat effect, solar module in laminating etc. of thermo-compression bonding etc. Deng heat effect etc., and make the resin combination of composition sealing material layer go bad, or deterioration or decompose.Assume the resin combination Comprising the dissolution such as additive or generate analyte, then they will act on the electromotive force face (element of solar cell device Face) so as to function, performance etc. are deteriorated.Therefore, thermostability is as the characteristic that the sealing material layer of solar module has It is requisite.
Additionally, the preferred moisture resistance of above-mentioned sealing material layer is excellent.In such a case it is possible to prevent from solar module Rear side moisture transmission, can prevent solar module photovoltaic cell burn into deterioration.
Above-mentioned sealing material layer is different from the filling oxidant layer being stacked on photovoltaic cell, it is not necessary to necessarily with transparent Property.The solar cell sealing material of present embodiment has above-mentioned characteristic, can be suitable as crystal type solaode mould It is the solar cell sealing material of the rear side of block, close intolerant to the solaode of the thin film solar cell module of moisture penetration Feng Cai.
The solar module of present embodiment, is not damaging in the range of the purpose of the present invention, can suitably have Arbitrary component.Typically, again reflecting layer, light expand can to arrange adhesive linkage, impact absorbing layer, coating layer, anti-reflection layer, the back side Scattered layer etc., but it is not limited to these.The position for arranging these layers is not particularly limited, it may be considered that arrange the purpose of such layer With the characteristic of such layer, arrange in position.
(solar module face side transparent protection member)
Solar module used by solar module face side transparent protection member, is not particularly limited, But due to the outermost layer positioned at solar module, therefore preferably have with against weather, water-repellancy, stain resistance, machinery Intensity is representative, for guaranteeing the performance of long-term reliability of the solar module in outdoor exposure.Additionally, in order to effective Utilize sunlight, the piece that preferably optical loss is little, the transparency is high.
As the solar module material of face side transparent protection member, can enumerate by polyester resin, fluororesin, Resin film, the glass substrate of the formation such as acrylic resin, cyclic olefin (co) polymer, vinyl-vinyl acetate copolymer Deng.Resin film is preferably in the excellent polyester resin of the aspects such as the transparency, intensity, cost, particularly poly terephthalic acid second two Good fluororesin of alcohol ester resin, against weather etc..As the example of fluororesin, there is tetrafluoroethylene-ethylene copolymer (ETFE), gather Fluoroethylene resin (PVF), polyvinylidene fluoride resin, polyflon (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), borontrifluoride ethylene chloride resin (PCTFE) is gathered.From from the viewpoint of against weather, polyvinylidene fluoride resin is excellent, but From against weather and mechanical strength consideration is had concurrently, tetrafluoroethylene-ethylene copolymer is excellent.Additionally, in order to improve and constituting sealing The cementability of the material of other layers such as material layer, preferred pair face side transparent protection member carries out sided corona treatment, corona treatment. In addition it is also possible to using the piece that stretch processing is implemented for improve mechanical strength, such as biaxial stretch-formed polypropylene foil.
In the case where glass substrate is used with face side transparent protection member as solar module, glass substrate The full light transmittance of wavelength 350～1400nm light be preferably more than 80%, more preferably more than 90%.As above-mentioned glass Glass substrate, generally uses the few blank glass of absorption in infrared portion, even if being backboard glass, as long as thickness be below 3mm then Impact to the output characteristics of solar module is few.Additionally, the mechanical strength in order to improve glass substrate, can be by heat Process to obtain strengthens glass, but it is also possible to using the kickboard glass of no heat treatment.Additionally, in order in the sensitive surface of glass substrate Lateral inhibition is reflected, it is also possible to carry out the coating of antireflection.
(solar module protects component with rear side)
Solar module used by solar module protects component with rear side, is not particularly limited, but by In the outermost layer positioned at solar module, therefore weatherability is required in the same manner as above-mentioned face side transparent protection member Each characteristics such as property, mechanical strength.Therefore, it can constitute solaode mould by the material same with face side transparent protection member Block protects component with rear side.That is, rear side protection component can also be used and used as face side transparent protection member Above-mentioned various materials.Especially, it may be preferred to using polyester resin and glass.Additionally, rear side protection component, due to not with Premised on the passing through of sunlight, therefore not necessarily require the transparency required in face side transparent protection member.Therefore, in order to Strengthen the mechanical strength of solar module, or for the deformation, the warpage that prevent from being caused by temperature change, enhancing can be puted up Plate.Strengthening plate can preferably use such as steel plate, plastic plate, FRP (fiberglass-reinforced plastic) plate etc..
Additionally, the solar cell sealing material of present embodiment can protect component with solar module rear side Integration.Protect component integrated by making solar cell sealing material and solar module rear side, can shorten Solar cell sealing material and solar module rear side protection component are cut into into module size in module assembled Operation.Additionally, by making to protect component to overlap respectively solar cell sealing material and solar module rear side Operation be operation with the piece overlapping of integration, it is also possible to shorten, omit and overlap operation.Make solar cell sealing material In the case of protecting component integrated with rear side with solar module, solar cell sealing material and solaode Module protects the laminating method of component with rear side, is not particularly limited.In laminating method, it is preferable to use cast molding machine, The known melt extruder such as extrusion panel forming machine, inflation forming machine, injection (mo(u)lding) machine is coextruded and is obtained laminated body Method；Melting or heated lamination another layer on a layer in advance comprising and the method that obtains laminated body.
In addition it is also possible to by using appropriate bonding agent (for example, maleic anhydride modified vistanex (three wells Learn trade name " ADOMER (registered trade mark) ", the trade name " MODIC (registered trade mark) " of Mitsubishi Chemical Ind of company system Deng), low (non-) the crystallinity soft polymer such as unsaturated polyolefin, with ethene/acrylic ester/maleic anhydride terpolymer (trade name " Bondine (registered trade mark) " of Zhu Hua CdF chemical companies etc.) be the acrylic acid series bonding agent of representative, ethylene/ Vinyl acetate based copolymer or the adhesive resin compositionss comprising them etc.) dry lamination method or lamination methods etc. come Lamination.
As bonding agent, preferably with the bonding agent of 120～150 DEG C or so of thermostability, specifically, preferably polyester System or urethane adhesive etc..Additionally, in order that the cementability raising of two layers, can implement such as silicon at least one layer Methane series coupling processing, titanium system coupling processing, sided corona treatment, corona treatment etc..
(solar cell device)
As long as the solar cell device used by solar module is available with the photovoltaic effect of quasiconductor and sends out The module of electricity, then be not particularly limited.Solar cell device can be (monocrystalline system, polycrystalline system, noncrystalline using such as silicon (amorphous) system) solaode, compound semiconductor (III-III races, II-VI group, other) solaode, the wet type sun Energy battery, organic semiconductor solaode etc..Wherein, from from the viewpoint of balance of power generation performance and cost etc., preferably Polycrystal silicon solaode.
Silicon solar cell element, compound semiconductor solar cell device all have as solar cell device Excellent characteristic, but known be easy to because damaged from outside stress, impact etc..The solar cell sealing of present embodiment Material is excellent due to flexibility, therefore absorbs stress, impact to solar cell device etc., prevents the broken of solar cell device The effect of damage is big.Therefore, in the solar module of present embodiment, by the solar cell sealing material of present embodiment The layer of formation is preferably directly engaged with solar cell device.Additionally, if solar cell sealing material has thermoplasticity, Even if after making solar module, it is also possible to take out solar cell device, therefore recirculation with comparalive ease It is excellent.Because the vinylite compositionss for constituting the solar cell sealing material of present embodiment have thermoplasticity, therefore make Also there is thermoplasticity for solar cell sealing material is overall, be also preferred from from the viewpoint of recirculation.
(metal electrode)
The composition and material of the metal electrode used by solar module, is not particularly limited, but in specific example, Laminated construction with nesa coating Yu metal film.Nesa coating is by SnO2, ITO, ZnO etc. formed.Metal film by silver, The metals such as gold, copper, stannum, aluminum, cadmium, zinc, hydrargyrum, chromium, molybdenum, tungsten, nickel, vanadium are formed.These metal films can be used alone, it is also possible to Alloy as Composite and use.Nesa coating is formed with metal film by methods such as CVD, sputtering, evaporations.
With regard to metal electrode, for example following methods can be enumerated：Welded using commonly known rosin series solder flux, water solublity The IPA (isopropyl alcohol) of agent, the aqueous solution of water, after electrode surface coating solder flux, are dried, then with heater, warm braw It is passed through the solder melted with solder fusing groove and melts liquid, in the surface-coated solder of metal electrode, is reheated and by the sun The method that energy cell device is engaged each other with metal electrode or metal electrode.In recent years, it is also adopted by direct in bonding station Coating solder flux and solder is only coated with solder, and solar cell device is engaged each other with metal electrode or metal electrode Method.
(manufacture method of solar module)
The manufacture method of the solar module of present embodiment is characterised by, including following operations：I () is by front Side transparent protection member, the solar cell sealing material of present embodiment, solar cell device (unit), solaode are close Envelope material and rear side protection component successively lamination and form the operation of laminated body, and the laminated body of gained is pressurizeed and is added by (ii) Heat and the operation of integration.
In operation (i), the face for preferably having concaveconvex shape (embossed shapes) with the formation of solar cell sealing material becomes The mode of solar cell device side is configured.
In operation (ii), conventionally using vacuum laminator or hot press, the lamination that will be obtained in operation (i) Body is heated and pressurizeed and integrated (sealing).In sealing, due to the resiliency of the solar cell sealing material of present embodiment Height, therefore the damage of solar cell device can be prevented.Further, since out gassing is good, being involved in so also without air, The product that high-quality can be well manufactured with yield rate.
When solar module is manufactured, the ethene-alpha-olefin system resin combination of composition solar cell sealing material is made Thing crosslinking curing.The cross-linking process step can be with operation (ii) while carrying out, it is also possible to carry out after operation (ii).
In the case of carrying out cross-linking process step after operation (ii), in operation (ii), in 125～160 DEG C of temperature, vacuum Heating in vacuum 3～6 minutes under conditions of below the support of pressure 10；Then, the pressurization under the atmospheric pressure of 1～15 minute or so is carried out, By the integration of above-mentioned laminated body.The cross-linking process step carried out after operation (ii) can be carried out by general method, for example, can be with Stove is crosslinked using the continuous way of tunnel type, it is also possible to using board-like batch (-type) crosslinking stove.Additionally, cross linking conditions are usually 130～155 DEG C carry out 20～60 minutes or so.
On the other hand, with operation (ii) while carrying out cross-linking process step in the case of, make the heating-up temperature in operation (ii) For 145～170 DEG C, make pressing time under atmospheric pressure be 6～30 minutes, in addition can with carry out after operation (ii) The situation of cross-linking process step is similarly operated and carried out.The solar cell sealing material of present embodiment is by containing specific organic Peroxide and there is excellent crosslinking feature, the bonding process of two-stage is needed not move through in operation (ii), can be in height Terminate at short notice under temperature, it is convenient to omit the cross-linking process step carried out after operation (ii), can significantly improve module Productivity.
In any case, the manufacture of the solar module of present embodiment, if do not decompose on Low molecular weight and In the such temperature of solar cell sealing material melting of present embodiment, glue temporarily in solar cell device, protected material Solar cell sealing material is connect, is then heated up and is carried out the crosslinking of sufficient bonding and sealing material.Selection can meet each Additive formulations as condition, for example, as long as selecting species and the impregnation of above-mentioned cross-linking agent and above-mentioned crosslinking coagent etc. Amount.
Additionally, above-mentioned crosslinking be preferably carried out to the gel fraction of the ethene-alpha-olefin copolymer after being crosslinked be changed into 50～ 95% degree.Gel fraction is more preferably 50～90%, more preferably 60～90%, most preferably 65～90%.It is solidifying Calculating for glue point rate can be carried out by following methods.For example, the sample of sealing material piece is taken from solar module 1g, the Soxhlet carried out in boiling toluene is extracted 10 hours.Extracting solution is filtered with 30 mesh stainless (steel) wires, by net at 110 DEG C Carry out 8 hours drying under reduced pressure.Measure remains in the weight of online remnant, and the weight for remaining in online remnant is relative Gel fraction is set in the ratio (%) of the sample size (1g) of before processing.
If above-mentioned gel fraction is more than above-mentioned lower limit, the thermostability of solar cell sealing material becomes good, Can suppress for example the high intensity xenon exposure experiment of the constant temperature and moisture test of 85 DEG C × 85%RH, 83 DEG C of black disk temperature, -40 DEG C～ The reduction of the cementability in 90 DEG C of thermal cycling test, heat resistant test.On the other hand, if gel fraction be above-mentioned higher limit with Under, then become the solar cell sealing material with high flexibility, the temperature tracing ability in -40 DEG C～90 DEG C of thermal cycling test Improve, therefore can prevent to peel off.
(generating equipment)
Productivity, generating efficiency, the life-span of the solar module of present embodiment etc. are excellent.Therefore, this has been used Cost, generating efficiency, the life-span of the generating equipment of the solar module of sample etc. are excellent, with value high in practicality.On The generating equipment stated, it is no matter outdoor, be suitable for life-time service within doors, for example it is arranged at the roof in house, as towards camping The portable power source of outdoor activities and by the use of, utilize as the accessory power supply of automobile batteries group.
Embodiment
Hereinafter, the present invention is specifically described based on embodiment, but the present invention is not limited to these embodiments.
(1) assay method
[content ratio of ethylene unit and alpha-olefin unit]
Sample 0.35g heating for dissolving and solution glass filter (G2) mistake for obtaining in hexachlorobutadiene 2.0ml will be made After filter, deuterated benzene 0.5ml is added, in being fitted into the NMR pipes of internal diameter 10mm.Using the JNM GX-400 types of NEC company NMR determines device, carries out at 120 DEG C13C-NMR is determined.Cumulative number is more than 8000 times.According to gained13C-NMR spectrum, The content ratio and the content ratio of alpha-olefin unit of the ethylene unit in quantitative copolymer.
[MFR]
According to ASTM D1238, the MFR of ethene-alpha-olefin copolymer is determined under conditions of 190 DEG C, 2.16kg loadings.
[density]
According to ASTM D1505, the density of ethene-alpha-olefin copolymer is determined.
[Xiao A hardness]
Ethene-alpha-olefin copolymer is heated 4 minutes at 190 DEG C, after being pressurizeed with 10MPa, with 5 points of 10MPa pressurizations cooling Clock obtains the thick pieces of 3mm until room temperature.Piece obtained by use, according to ASTM D2240, determines ethene-alpha-olefin copolymer Xiao A hardness.
[weathering test]
The piece of gained is cut into after the size of 12cm × 7.5cm, using not having in the range of 350～800nm of wavelength There is the blank glass (thickness 3.2mm) for absorbing domain, according to blank glass/solar cell sealing material/white on the blank glass The piece sample of the solar cell sealing material of 500 μm of the order laminated thickness of glass sheet, with 150 DEG C, vacuum 5 minutes, pressurization 5 points Clock is laminated and is crimped with laminater (NPC societies system, LM-110X160S).Then, kept for 45 minutes in 150 DEG C of baking oven, system Make laminated body.
Next, for above-mentioned laminated body, using the promotion weathering test machine using metal halide lamp as light source (KU-R5NW, Daipla Wintes societies system), in the air of 80 DEG C of temperature, the uitraviolet intensity irradiated under 300～400nm is 1000W/m 2Ultraviolet take out after 250 hours.
During the transparency is evaluated, for the accelerated test sample of gained, using the spectrophotometric in Hitachi's company system The spectrophotometer of the integrating sphere of φ 150mm is installed on meter (trade name " U-3010 "), the wavelength zone of 350～800nm is determined The full light transmittance of light splitting of the piece sample in domain, above-mentioned laminated body.And, by measurement result be multiplied by standard light D65 and Standard luminescent efficiency V (λ), calculates the full light transmittance (Tvis) of visible ray.
The difference of the absorbance before and after test under the 450nm of the laminated body obtained by evaluation.
○：The difference of absorbance is less than 5%
△：The difference of absorbance is more than 5% and for less than 8%
×：The difference of absorbance is more than 8%
(2) synthesis of ethene-alpha-olefin copolymer
(synthesis example 1)
Supplied with the ratio of 8.0mmol/hr in a supply mouth of the continuous polymerization device of the internal volume 50L for possessing agitator As the toluene solution of the MAO of co-catalyst, supplied as the double of major catalyst using the ratio of 0.025mmol/hr The hexane slurry of (1,3- dimethylcyclo-pentadienyl) zirconium dichloride, with the ratio of 0.5mmol/hr oneself of triisobutyl aluminium is supplied Alkane solution, becomes 20L/hr's using the total of normal hexane using as catalyst solution and polymer solvent, being dehydrated after refining Mode continuously feeds the normal hexane after dehydration is refined.Simultaneously other supply mouths in polymerizer are continuously supplied with the ratio of 3kg/hr 1-butylene is continuously supplied to ethylene, with the ratio of 15kg/hr, hydrogen is continuously supplied with the ratio of 5NL/hr, in polymerization temperature 90 DEG C, gross pressure 3MPaG carries out continuous solution polymerization under conditions of 1.0 hours holdup times.Make in polymerizer generate ethylene- Normal hexane/the toluene mixed solution of alpha olefin copolymer is continuously discharged via the outlet for being arranged at polymerizer bottom, is led Enter to chuck portion with 3～25kg/cm2In the connecting tube being heated by steam, so that the normal hexane of ethene-alpha-olefin copolymer/ Toluene mixed solution becomes 150～190 DEG C.
In addition, the supply mouth for injection as the methanol of catalyst deactivator was set up before it will reach connecting tube, With the speed of about 0.75L/hr injection methanol and normal hexane/toluene mixed solution for collaborating in ethene-alpha-olefin copolymer.In band The connecting tube inside holding of steam jacket passes through in the normal hexane/toluene mixed solution of about 190 DEG C of ethene-alpha-olefin copolymer The aperture of the pressure-control valve that adjustment is arranged at connecting tube terminal part makes it maintain about 4.3MpaG, so as to be continuously fed to dodge In steaming groove.In addition, in the transfer in flash tank, solution temperature and the setting of pressure-regulating valve aperture are carried out, so that flash tank Interior pressure maintains the temperature in the steam portion in about 0.1MPaG, flash tank to maintain about 180 DEG C.Then, by the way that die head temperature is set Due to 180 DEG C of single axle extruding machine, with tank strands are cooled down, with granule pelleter strands are cut off, obtain as granule ethylene- Alpha olefin copolymer.Yield is 2.2kg/hr.Physical property is shown in Table 1.
(synthesis example 2)
Respectively using the ratio of 0.012mmol/hr supply as major catalyst [dimethyl (tert-butylamides) (tetramethyl- η 5- cyclopentadienyl groups) silane] titanium chloride hexane solution, using the supply of the ratio of 0.05mmol/hr as the three of co-catalyst Phenyl carbonsThe toluene solution of (four pentafluorophenyl groups) borate, with the hexane that the ratio of 0.4mmol/hr supplies triisobutyl aluminium Solution, and hydrogen is supplied with the ratio supply 1-butylene of 5kg/hr, with the ratio of 100NL/hr, in addition with above-mentioned synthesis Example 1 is similarly operated and obtains ethene-alpha-olefin copolymer.Yield is 1.3kg/hr.Physical property is shown in Table 1.
(synthesis example 3)
Respectively double (p-methylphenyl) methylene (cyclopentadiene as major catalyst are supplied using the ratio of 0.003mmol/hr Base) (1, Isosorbide-5-Nitrae, 4,7,7,10,10- prestox -1,2,3,4,7,8,9,10- octahydros dibenzo (b, h)-fluorenyl) zirconium dichloride Hexane solution, supplies the toluene solution as the MAO of co-catalyst, with 0.6mmol/ using the ratio of 3.0mmol/hr The ratio of hr supplies the hexane solution of triisobutyl aluminium；Ethylene is supplied with the ratio of 4.3kg/hr；Replace 1-butylene and with The ratio supply 1- octenes of 6.4kg/hr；After the dehydration used using 1- octenes and as catalyst solution and polymer solvent is refined Normal hexane total mode for becoming 20L/hr continuously feed dehydration it is refined after normal hexane；Supplied with the ratio of 40NL/hr To hydrogen；And polymerization temperature is made for 130 DEG C, operate in the same manner as synthesis example 1 in addition and obtain ethene-alpha-olefin copolymerization Thing.Yield is 4.3kg/hr.Physical property is shown in Table 1.
[table 1]
Synthesis example 1 Synthesis example 2 Synthesis example 3
The species of alpha-olefin 1-butylene 1-butylene 1- octenes
The content ratio [mol%] of alpha-olefin unit 14 17 11
The content ratio [mol%] of ethylene unit 86 83 89
MFR [g/10 minutes] 20 11 48
Shore A Hardness [-] 70 62 84
Density [g/cm3] 0.870 0.886 0.884
(3) manufacture of solar cell sealing material (piece)
(embodiment 1)
Relative to the weight portion of ethene-alpha-olefin copolymer 100 of synthesis example 1,1 point as organic peroxide is coordinated Clock half life temperature is 166 DEG C of the weight portion of tert-butyl hydroperoxide -2- ethylhexyl carbonates 1.0, purple as enumerate BTA system 2- (2H-1,2, the 3- benzotriazole -2- bases) weight portion of -6- dodecyl -4- methylphenols 0.3 of ultraviolet absorbers, as silicon It is the weight portion of 3- methacryloxypropyl trimethoxy silanes 0.5 of alkane coupling agent, different as the triallyl of crosslinking coagent The weight portion of cyanurate 1.2, as double (2,2,6, the 6- tetramethyl -4- piperidyls) sebacates for the amine system light stabilizer that is obstructed 0.2 weight portion, as octadecyl -3- (3, the 5- di-tert-butyl-hydroxy phenyl) propionic ester 0.05 of hindered phenol series stabilizer Weight portion, as three (2,4- di-tert-butyl-phenyl) weight portions of phosphite ester 0.1 of phosphorus system stabilizer.
Clothes hanger is installed on the single axle extruding machine (screw diameter 20mm φ, L/D=28) of Thermo plastic company systems Formula T-shaped mould head (die lip shape：270 × 0.8mm), under conditions of 100 DEG C of die head temperature, with 30 DEG C of roll temperature, winding speed 1.0m/min, chill roll carries out molding using dandy roll, obtains embossing piece (the solar cell sealing material of 500 μm of maximum gauge Piece).The voidage of the piece of gained is 28%.The various evaluation results of the piece of gained are shown in Table 2.
(embodiment 2～4)
The cooperation being set to shown in table 2, in addition, operates in the same manner as the above embodiments 1 and obtains the embossing piece (sun Energy cell sealing material piece).The voidage all 28% of the piece of gained.The various evaluation results of the piece of gained are shown in Table 2.
(comparative example 1)
The cooperation being set to shown in table 2, in addition, operates in the same manner as the above embodiments 1 and obtains the embossing piece (sun Energy cell sealing material piece).The voidage all 28% of the piece of gained.The various evaluation results of the piece of gained are shown in Table 2.
[table 2]
UV absorbent 1：2- (2H-1,2,3- benzotriazole -2- bases) -6- dodecyl -4- methylphenols
UV absorbent 2：2- (2H-1,2,3- benzotriazole -2- bases) -4,6- di-tert-pentyl phenols
UV absorbent 3：2,2 '-di-2-ethylhexylphosphine oxide [6- (2H-1,2,3- benzotriazole -2- bases) -4- (1,1,3,3- tetra- Methyl butyl) phenol]
UV absorbent 4：2- hydroxyl -4- n-octyl epoxide benzophenone
The application advocate by June 19th, 2012 propose Japanese patent application laid be willing to 2012-138261 based on it is excellent First weigh, the entire disclosure is incorporated into herein.

Claims (11)

1. a kind of solar module, it possesses：
Face side transparent protection member,
Rear side protects component,
Solar cell device, and
Sealant, the sealant is formed by being crosslinked solar cell sealing material, and by the solar cell device It is sealed between the face side transparent protection member and rear side protection component,
The solar cell device is the tandem type solar cell device by silicon metal and amorphous silicon lamination,
The solar cell sealing material is comprising ethene-alpha-olefin copolymer, organic peroxide and UV absorbent Solar cell sealing material,
The UV absorbent is shown in the enumerate BTA system UV absorbent shown in following formulas (1), following formulas (2) Enumerate BTA system UV absorbent or 2,2 '-di-2-ethylhexylphosphine oxide [6- (2H-1,2,3- benzotriazole -2- bases) -4- (1,1,3, 3- tetramethyl butyls) phenol],
In formula, R1Represent hydrogen atom, R2～R4It is mutually different, represent that hydrogen atom, the alkyl of carbon number 1～20, hydroxyl, carbon are former The alkoxyl of subnumber 1～22 or the alkyloxycarbonyl of carbon number 1～22,
In formula, R1Represent hydrogen atom, R5～R8It is identical or different, represent hydrogen atom, the alkyl of carbon number 1～20, hydroxyl, carbon The alkoxyl of atomic number 1～22 or the alkyloxycarbonyl of carbon number 1～22, R5With R8It is identical, R6With R7It is identical,
In the solar cell sealing material, the content of the UV absorbent is relative to the ethene-alpha-olefin copolymerization The weight portion of thing 100 is 0.1～4.5 weight portion.
2. solar module according to claim 1, the ethene-alpha-olefin copolymer meets following important document A1)～a4),
A1) content ratio from the Component units of ethylene is 80～90mol%, from the α-alkene of carbon number 3～20 The content ratio of the Component units of hydrocarbon is 10～20mol%；
A2) according to ASTM D1238, it is 10～50g/10 point that the MFR for obtaining is determined under conditions of 190 DEG C, 2.16kg loadings Clock；
A3 it is 0.865～0.884g/cm that the density for obtaining) is determined according to ASTM D15053；
A4 it is 60～85 that the Xiao A hardness for obtaining) is determined according to ASTM D2240.
3. solar module according to claim 1, according to ASTM D1238, in 190 DEG C, the bar of 2.16kg loadings The MFR that the ethene-alpha-olefin copolymer for obtaining is determined under part is 10～27g/10 minutes.
4. solar module according to claim 1,1 minute half life temperature of the organic peroxide is 100～170 DEG C, and the content of the organic peroxide described in the solar cell sealing material relative to the ethylene- The weight portion of alpha olefin copolymer 100 is 0.1～3 weight portion.
5. solar module according to claim 1, the solar cell sealing material relative to the ethylene-α- The weight portion of olefin copolymer 100, further comprising the weight portion of silane coupler 0.1～5.
6. solar module according to claim 1, the solar cell sealing material relative to the ethylene-α- The weight portion of olefin copolymer 100, further comprising the weight portion of hindered phenol series stabilizer 0.005～0.1.
7. solar module according to claim 1, the solar cell sealing material relative to the ethylene-α- The weight portion of olefin copolymer 100, further comprising the weight portion of amine system light stabilizer 0.01～2.0 that is obstructed.
8. solar module according to claim 1, the solar cell sealing material relative to the ethylene-α- The weight portion of olefin copolymer 100, further comprising the weight portion of phosphorus system stabilizer 0.005～0.5.
9. solar module according to claim 1, the solar cell sealing material relative to the ethylene-α- The weight portion of olefin copolymer 100, further comprising the weight portion of crosslinking coagent 0.05～5.
10. solar module according to claim 1, the solar cell sealing material is by by the second After alkene-alpha olefin copolymer, the organic peroxide and the UV absorbent melting mixing, lamellar ground extrusion molding and Obtain.
11. solar modules according to claim 1, the solar cell sealing material is lamellar.
CN201380031931.1A 2012-06-19 2013-05-21 Solar cell sealing material and solar cell module Active CN104380481B (en)

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CN102115643A (en) * 2010-12-31 2011-07-06 广州鹿山新材料股份有限公司 Novel solar cell packaging adhesive film

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