CN107429013A - Diaphragm seal and solar module - Google Patents
Diaphragm seal and solar module Download PDFInfo
- Publication number
- CN107429013A CN107429013A CN201680014679.7A CN201680014679A CN107429013A CN 107429013 A CN107429013 A CN 107429013A CN 201680014679 A CN201680014679 A CN 201680014679A CN 107429013 A CN107429013 A CN 107429013A
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- China
- Prior art keywords
- diaphragm seal
- compound
- methyl
- formula
- mass parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 vinyl aromatic compounds Chemical class 0.000 claims abstract description 60
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- 230000006835 compression Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N dimethyl benzenedicarboxylate Natural products COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IDLQNWHZCUKJCQ-UHFFFAOYSA-N ethene ethenyl octadecanoate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)OC=C.C=C IDLQNWHZCUKJCQ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- CXQRNYIKPJXYLU-ZHBVTVBMSA-N pinidine Chemical compound C\C=C\[C@H]1CCC[C@@H](C)N1 CXQRNYIKPJXYLU-ZHBVTVBMSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical class OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
-
- 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
- H01L31/049—Protective back sheets
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Sealing Material Composition (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The diaphragm seal of the present invention is the diaphragm seal for sealing solar cell device, and it is included：Ethylene polar monomer copolymer；Crosslinking agent；One or two or more kinds of crosslinking coagents in the group being made up of di vinyl aromatic compounds of group, cyanurate compound, diallyl compound, triallyl compound, oxime compound and maleimide compound；And selected from least one of two (methyl) acrylate compounds represented by following formula (I)s and the diacrylate compounds represented by following formula (II)s compound.Here, in above-mentioned formula (I), R1And R3It is each independently hydrogen atom or methyl, R2For methyl, m+n is less than more than 17 integer.Here, in above-mentioned formula (II), k is less than more than 13 integer.
Description
Technical field
The present invention relates to diaphragm seal and solar module.
Background technology
In recent years, the energy as cleaning, solar power generation is noticeable, is promoting the solar energy of solar power generation
The exploitation of battery module.Solar module is generally following to be formed：Protective glass (face side transparent protection member), sealing
Piece, solar cell device, diaphragm seal, backboard (rear side protection component).In the manufacture of solar module, by
Diaphragm seal is heated in the state of above layers are laminated, solar cell is sealed so as to the resin melting in diaphragm seal
Element, so it is Nian Jie with protective glass, backboard.
As the diaphragm seal of solar cell device, all the time, vinyl-vinyl acetate copolymer (EVA) piece by
It is excellent in the transparency, flexibility, processability and durability etc. and be widely used.For example, (the Japanese Unexamined Patent Publication 2010- of patent document 1
No. 53298 publications) in, disclose formed by the EVA compositions comprising crosslinking agent and trimellitic acid ester, cementability and film
The property excellent diaphragm seal of both of which.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2010-53298 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-53379 publications
The content of the invention
Invent problem to be solved
With large solar power station (Mega Solar) popularization, for the purpose of reducing transmission loss,
The Towards Higher Voltage of propulsion system voltage.In the solar module used in the state of maintaining high voltage, it some times happens that
Output is greatly reduced and PID (Potential Induced Degradation (potential induction attenuation) letters of deterioration in characteristics
Write) phenomenon.
Here, according to the research of the present inventor etc., for example, specify that by making diaphragm seal contain such as (the Japan of patent document 2
JP 2008-53379 publications) described in such (methyl) acrylate compounds, solar module can be suppressed
PID phenomenons generation.
But specify that, it is close in the shaping of diaphragm seal if making diaphragm seal contain (methyl) acrylate compounds
The dispersiveness variation of the constituent of mounting.Further it specify that, in the keeping of diaphragm seal, each constituent can also ooze sometimes
Go out.Additionally it specify that, because the resistance to incipient scorch of the resin combination before sheetmolding is also deteriorated, therefore the processability of diaphragm seal
It is deteriorated.
The present invention is to propose in view of the foregoing, there is provided can suppress the hair of the PID phenomenons of solar module
The raw and diaphragm seal of keeping quality and excellent in workability.
For solving the method for problem
The present inventor etc. in order to the generation for the PID phenomenons that can suppress solar module is provided and keeping quality and add
The excellent diaphragm seal of work and have made intensive studies.Its result is found, by using specific two (methyl) acroleic acid esterifications
Constituent of the compound as diaphragm seal, the generation of the PID phenomenons of solar module can be suppressed, further, it is possible to improve
The resistance to incipient scorch of resin combination before sheetmolding, and then can prevent that each constituent oozes out in the keeping of diaphragm seal, with
To completing the present invention.
That is, according to the present invention, there is provided diaphragm seal and solar module as shown below.
[1]
A kind of diaphragm seal, is the diaphragm seal for sealing solar cell device, and it is included：
Ethylene-polar monomer copolymer,
Crosslinking agent,
Selected from by di vinyl aromatic compounds of group, cyanurate compound, diallyl compound, triallyl chemical combination
One or two or more kinds of crosslinking coagents in the group of thing, oxime compound and maleimide compound composition, and
Selected from two (methyl) acrylate compounds represented by following formula (I)s and two propylene represented by following formula (II)s
At least one of ester compound compound.
[changing 1]
(in above-mentioned formula (I), R1And R3It is each independently hydrogen atom or methyl, R2For methyl, m+n is less than more than 17
Integer)
[changing 2]
(in above-mentioned formula (II), k is less than more than 13 integer)
[2]
According to the diaphragm seal described in above-mentioned [1], above-mentioned ethylene-polar monomer copolymer is total to comprising ethane-acetic acid ethyenyl ester
Polymers.
[3]
According to the diaphragm seal described in above-mentioned [2], vinyl acetate is derived from above-mentioned vinyl-vinyl acetate copolymer
The content ratio of construction unit be below the mass % of more than 10 mass % 47.
[4]
According to the diaphragm seal any one of above-mentioned [1]~[3], the R in above-mentioned formula (I)1And R3It is hydrogen atom.
[5]
According to the diaphragm seal any one of above-mentioned [1]~[4], the m+n in above-mentioned formula (I) is 2 or 3.
[6]
According to the diaphragm seal any one of above-mentioned [1]~[3], the k in above-mentioned formula (II) is 3.
[7]
According to the diaphragm seal any one of above-mentioned [1]~[6], selected from two (methyl) third represented by above-mentioned formula (I)
The content of at least one of enoic acid ester compounds and the diacrylate compounds that are represented by above-mentioned formula (II) compound is relative
Below the above-mentioned mass parts of ethylene-polar monomer copolymer 100 is more than 0.01 mass parts 3.0 mass parts.
[8]
A kind of solar module, it possesses：
Face side transparent protection member,
Rear side protects component,
Solar cell device, and
Sealant, it is made up of the cross-linking agent of the diaphragm seal any one of above-mentioned [1]~[7], also, by it is above-mentioned too
Positive energy cell device is sealed between above-mentioned face side transparent protection member and above-mentioned rear side protection component.
The effect of invention
According to the present invention it is possible to realize the generation for the PID phenomenons that can suppress solar module and keeping quality and add
The excellent diaphragm seal of work.
Brief description of the drawings
Above-mentioned purpose and other objects, features and advantages by the preferred embodiment of following record and its it is subsidiary with
Lower accompanying drawing and further clearly.
Fig. 1 is the sectional view for the representative embodiments for schematically showing the solar module of the present invention.
Embodiment
Hereinafter, embodiments of the present invention are illustrated using accompanying drawing.In addition, on number range " A~B ", such as
Fruit does not specialize, then it represents that more than A below B.In addition, " (methyl) acrylate " so-called in this specification, it is meant that " third
Olefin(e) acid ester " or " methacrylate ".In addition, " (methyl) acrylic acid " means " acrylic acid " or " methyl in this manual
Acrylic acid ".
1. on diaphragm seal
The diaphragm seal of present embodiment is the diaphragm seal for sealing solar cell device, and it is included：Ethylene-polar list
Precursor copolymer；Crosslinking agent；Selected from by di vinyl aromatic compounds of group, cyanurate compound, diallyl compound, triolefin
One or two or more kinds of crosslinking coagents in the group of compound, oxime compound and maleimide compound composition；With
And represent diacrylated selected from two (methyl) acrylate compounds represented by following formula (I)s and by following formula (II)s
At least one of compound compound.
[changing 1]
(in above-mentioned formula (I), R1And R3It is each independently hydrogen atom or methyl, R2For methyl, m+n is less than more than 17
Integer)
[changing 2]
(in above-mentioned formula (II), k is less than more than 13 integer)
The present inventor etc. can suppress generation and the diaphragm seal of keeping quality and excellent in workability of PID phenomenons in order to provide,
Have made intensive studies.Its result is found, by addition to ethylene-polar monomer copolymer, crosslinking agent and crosslinking coagent, going back
Use the diacrylate represented selected from two (methyl) acrylate compounds represented by above-mentioned formula (I) and by above-mentioned formula (II)
At least one of compound compound, it is possible to increase the resistance to incipient scorch of resin combination, and then gained diaphragm seal can be prevented
Keeping when each constituent ooze out.I.e., it is known that the keeping quality and processability of diaphragm seal can be improved.Furthermore, it was found that make
It can suppress the generation of PID phenomenons with the solar module of such diaphragm seal.
That is, for the diaphragm seal of present embodiment, its keeping quality and excellent in workability, and the gained sun can be suppressed
The generation of the PID phenomenons of energy battery module.
Hereinafter, each composition of the diaphragm seal to forming present embodiment illustrates.
＜ ethylene-polar monomer copolymers ＞
The diaphragm seal of present embodiment contains ethylene-polar monomer copolymer.
As above-mentioned ethylene-polar monomer copolymer, for example, selected from ethene-(methyl) ethyl acrylate is common
Polymers, ethene-(methyl) methyl acrylate copolymer, ethene-(methyl) propyl acrylate copolymer, ethene-(methyl) propylene
Butyl acrylate copolymer, ethene-(methyl) Hexyl 2-propenoate copolymer, ethene-(methyl) 2-Hydroxy ethyl acrylate copolymer,
Ethene-(methyl) 2-hydroxypropyl acrylate copolymer, ethene-(methyl) glycidyl acrylate copolymer, ethene-horse
Come dimethyl phthalate copolymer, ethylene maleic acid diethyl ester copolymer, ethene-dimethyl fumarate copolymer, ethene-fumaric acid
The ethene such as diethyl ester copolymer-unsaturated carboxylic acid ester copolymer；Ethene-(methyl) acrylic copolymer, ethylene maleic acid copolymerization
Ethene-the copolymers of unsaturated carboxylic acids such as thing, ethene-fumaric acid copolymer, ethene-crotonic acid-copolymers and their salt；Ethene-
Vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl butyrate ester copolymer, ethene-vinyl stearate
The ethylene-vinyl ester copolymers such as ester copolymer；One or two or more kinds in ethylene-styrene copolymer etc..
Wherein, as above-mentioned ethylene-polar monomer copolymer, obtain the balance of easiness and performance from it and consider, preferably
It is especially excellent comprising the one or two or more kinds in ethylene-vinyl ester copolymer, ethene-unsaturated carboxylic acid ester copolymer
Choosing includes vinyl-vinyl acetate copolymer.
Above-mentioned vinyl-vinyl acetate copolymer is the copolymer of ethene and vinyl acetate, usually random copolymer.
The content ratio of the construction unit from vinyl acetate in above-mentioned vinyl-vinyl acetate copolymer is preferred
For below the mass % of more than 10 mass % 47, more preferably more than 13 mass % below 35 mass %.If vinyl acetate
Within the range, then the cementability of diaphragm seal, weatherability, the transparency, the balance of engineering properties are more excellent for content.In addition, will be close
During mounting film forming, film forming is also good.
Vinyl acetate content can determine according to JIS K6730.
In addition, bipolymer of the vinyl-vinyl acetate copolymer preferably only comprising ethene and vinyl acetate, but
In addition to ethene and vinyl acetate, it can also include and be selected from vinyl formate, ethylene glycolate, vinyl propionate
The vinyl esters such as ester, vinyl benzoate system monomer, acrylic acid, methacrylic acid, ethylacrylic acid or their salt or alkane
One or two or more kinds in acrylic monomers such as base ester etc. are as copolymer composition.Beyond comprising ethene and vinyl acetate
Above-mentioned copolymer composition in the case of, preferably make beyond the ethene and vinyl acetate in vinyl-vinyl acetate copolymer
The amount of above-mentioned copolymer composition is below the mass % of more than 0.5 mass % 5.
By the melt flow of the obtained vinyl-vinyl acetate copolymers under 190 DEG C, 2160g load of ASTM D 1238
Dynamic speed is preferably below 5g/10 minute above 45g/10 minutes, more preferably below 5g/10 minute above 40g/10 minutes,
More preferably below 10g/10 minute above 30g/10 minutes.
If the MFR of vinyl-vinyl acetate copolymer is above range, extrusion molding is excellent.Ethylene-acetate second
The polarity in polymerization temperature, polymerization pressure and polymerization system when the MFR of enoate copolymer can be by adjusting polymerisation
The monomer concentration of monomer and the molar ratio of hydrogen concentration etc. adjust.
The diaphragm seal of present embodiment can use 2 kinds different such as vinyl acetate content, melt flow rate (MFR)
Vinyl-vinyl acetate copolymer above, in the case of using two or more vinyl-vinyl acetate copolymer, preferably make
Their total amount is above range.
On the content of above-mentioned ethylene-polar monomer copolymer, set by the entirety of the resin component contained by the diaphragm seal
For 100 mass % when, preferably more than 80 mass %, more preferably more than 90 mass %, more preferably 95 mass % with
On, and it is particularly preferred to be 100 mass %.Thereby, it is possible to obtain the transparency, cementability, heat resistance, flexibility, outward appearance, friendship
Join the more excellent diaphragm seal of the balance of each characteristics such as characteristic, electrical characteristic and extrusion molding.
On the content of above-mentioned resin component, when the entirety of the diaphragm seal is set into 100 mass %, preferably 50 matter
Measure more than %, more preferably more than 70 mass %, more preferably more than 80 mass %, particularly preferably 90 mass % with
On.Thereby, it is possible to obtain the transparency, cementability, heat resistance, flexibility, outward appearance, crosslinking feature, electrical characteristic and extrusion molding
Property etc. each characteristic the more excellent diaphragm seal of balance.
The manufacture method of above-mentioned ethylene-polar monomer copolymer is not particularly limited, and can be made by known method
Make.For example, can be by the presence of radical initiators, at 500~4000 atmospheric pressure, 100~300 DEG C, molten
In the presence of agent, chain-transferring agent or in the absence of, ethene, polar monomer, other copolymer compositions as needed is copolymerized to make
Make.
＜ crosslinking agents ＞
, can be with use example such as organic peroxide as crosslinking agent.
In the diaphragm seal of present embodiment, by containing crosslinking agent, above-mentioned ethylene-polar monomer copolymer can be handed over
Connection, or silane coupler can be grafted on to above-mentioned ethylene-polar monomer copolymer.By the way that above-mentioned ethylene-polar monomer is total to
Polymers is crosslinked, and becomes good so as to heat resistance, the weatherability of gained diaphragm seal.
The content of crosslinking agent in diaphragm seal is relative to the mass parts of ethylene-polar monomer copolymer 100, preferably 0.1 matter
Measure more than part below 5 mass parts, more preferably more than 0.2 mass parts below 2 mass parts, more preferably 0.2 mass parts with
Below upper 1 mass parts.If the content of crosslinking agent is more than above-mentioned lower limit, the drop of the crosslinking feature of diaphragm seal can be suppressed
It is low so that the graft reaction of silane coupler and the main chain of ethylene-polar monomer copolymer is good, can suppress heat resistance, glue
The reduction of connecing property.If in addition, the content of crosslinking agent be above-mentioned higher limit below, the yield of catabolite of crosslinking agent etc.
More reduce, can more reliably suppress to produce bubble in diaphragm seal.
In view of the productivity ratio of solar module, as organic peroxide, preferably half-life period is less than 10 hours
And decomposition temperature is less than 105 DEG C of organic peroxide.In addition, from the aspect of security, preferably up to storage temperature is
More than 10 DEG C of organic peroxide.As the example of such organic peroxide, it can use and be selected from the bay of peroxidating two
Acyl, 1,1,3,3- tetramethyl butyls peroxidating -2 ethyl hexanoic acid ester, dibenzoyl peroxide, cyclohexanone peroxide, diperoxy
Tert-butyl o phthalic acid ester, cumyl hydroperoxide, the TBHP, (t-butyl peroxies of 2,5- dimethyl -2,5- two
Change) hexene, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexane, peroxidating tertiary pentyl -2 ethyl hexanoic acid ester, peroxidating
The tert-butyl group -2 ethyl hexanoic acid ester, peroxidating tert-butyl isobutyrate, peroxidating Malaysia the tert-butyl acrylate, (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, (the tert-butyl hydroperoxide) -3,3,5- of 1,1- bis- 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 peroxide) hexane, peroxide acid tert-amyl acetate, peroxide acetic acid butyl ester, the different nonanoic acid ter-butyl ester of peroxidating, mistake
Aoxidize t-butyl perbenzoate, 2,2- bis- (butyl peroxy) butane, normal-butyl -4,4- two (tert-butyl hydroperoxide) butyrate, mistake
Oxidation methyl ethyl ketone, ethyl -3,3- two (tert-butyl hydroperoxide) butyrate, cumyl peroxide, tert-butyl peroxide are different
Propyl benzene, peroxidized t-butyl perbenzoate, di-tert-butyl peroxide, 1,1,3,3- tetramethyl butyl hydroperoxides, peroxidating second
One or two or more kinds in acyl acetone etc..
Wherein, preferably using selected from 2,5- dimethyl -2,5- bis- (tert-butyl hydroperoxide) hexene, 2,5- dimethyl -2,5-
Two (tert-butyl hydroperoxide) hexanes, one kind in tert-butyl hydroperoxide -2- ethylhexyl carbonates, peroxidized t-butyl perbenzoate
Or more than two kinds.
The diaphragm seal of present embodiment is needed not move through true by having excellent crosslinking feature containing crosslinking agent
The two stage bonding process of dead level press and crosslinking stove, and can be completed in high-temperature with the short time.
＜ crosslinking coagents ＞
As crosslinking coagent, it can use and be selected from by di vinyl aromatic compounds of group, cyanurate compound, two allyls
One or two or more kinds in the group that based compound, triallyl compound, oxime compound and maleimide compound form.
The content of crosslinking coagent in diaphragm seal is relative to the mass parts of ethylene-polar monomer copolymer 100, and preferably 5.0
Below mass parts, more preferably below 3.0 mass parts, particularly preferably below 2.0 mass parts.
In addition, the content of the crosslinking coagent in diaphragm seal is relative to the mass parts of ethylene-polar monomer copolymer 100, preferably
More than 0.1 mass parts, more preferably more than 0.3 mass parts, more preferably more than 0.5 mass parts.Thus, it is possible to formed
The cross-linked structure of appropriateness, it is possible to increase heat resistance, mechanical properties and the cementability of diaphragm seal.
As di vinyl aromatic compounds of group, can enumerate such as divinylbenzene, two-isopropenylbenzene.
As cyanurate compound, can enumerate such as triallyl cyanurate, triallyl isocyanurate.
As diallyl compound, can enumerate such as diallyl phthalate.
As triallyl compound, can enumerate such as pentaerythritol triallyl ether.
As oxime compound, such as paraquinonedioxime, p-p '-dibenzoyl quininie dioxime etc. can be enumerated.
As maleimide compound, can enumerate such as metaphenylene dimaleimide.
(methyl) acrylate compounds of ＜ bis- ＞
The diaphragm seal of present embodiment contain selected from two (methyl) acrylate compounds that are represented by following formula (I)s and by
At least one of the diacrylate compounds that following formula (II)s represent compound.
[changing 1]
In above-mentioned formula (I), R1And R3It is each independently hydrogen atom or methyl, R2For methyl, m+n is less than more than 17
The integer of the integer of integer, more preferably less than more than 14, particularly preferably less than more than 13.
[changing 2]
In above-mentioned formula (II), k be less than more than 13 integer, preferably less than more than 23 integer, more preferably 3.
In the diaphragm seal of present embodiment, by two (methyl) acrylate compounds of above-mentioned formula (I) expression and by upper
The diacrylate compounds for stating formula (II) expression can be used alone or be applied in combination more than two kinds.
If comprising selected from two (methyl) acrylate compounds represented by above-mentioned formula (I) and by above-mentioned formula (II) expression
At least one of diacrylate compounds compound, then can improve the resistance to PID performances of gained solar module.
It is preferred that the R in above-mentioned formula (I)1And R3It is hydrogen atom.
If R2For methyl, then diaphragm seal shaping when it is dispersed excellent.
In addition, as two (methyl) acrylate compounds represented by above-mentioned formula (I), from disperseing when sealing sheetmolding
From the viewpoint of the balance of the resistance to incipient scorch of property and resin combination is more excellent, preferably DPG two (methyl) acrylic acid
Ester, more preferably tripropylene glycol two (methyl) acrylate, propylene glycol diacrylate, tripropylene glycol diacrylate.
In addition, from during the shaping of diaphragm seal it is dispersed it is excellent from the viewpoint of, m+n in preferably above-mentioned formula (I) for 2 or
3.In such a case it is possible to be the mixture of compound and the m+n compounds for being 3 that m+n is 2,30 matter can also be mixed with
The m+n for measuring below % is the compound beyond 2 or 3.
In addition, as the diacrylate compounds represented by above-mentioned formula (II), from sealing sheetmolding when dispersiveness and
From the viewpoint of the balance of the resistance to incipient scorch of resin combination is more excellent, preferably diethylene glycol diacrylate, three second two
Alcohol diacrylate, more preferably triethylene glycol diacrylate.
In addition, from during the shaping of diaphragm seal it is dispersed it is excellent from the viewpoint of, k in preferably above-mentioned formula (II) is 3.
In this case, can be with the mixture that k is compound beyond 3, the k below 30 mass % can also be mixed with as beyond 3
Compound.
The content of two (methyl) acrylate compounds represented by above-mentioned formula (I) is copolymerized relative to ethylene-polar monomer
The mass parts of thing 100, preferably more than 0.05 mass parts below 3.0 mass parts, 2.0 mass parts more preferably more than 0.1 mass parts
Hereinafter, particularly preferably more than 0.1 mass parts below 1.0 mass parts.If the content of two (methyl) acrylate compounds is
More than above-mentioned lower limit, then the PID patience of gained solar module can be made better.If in addition, two (methyl) third
The content of enoic acid ester compounds is below above-mentioned higher limit, then the resistance to incipient scorch of diaphragm seal can be made better.
The content of the diacrylate compounds represented by above-mentioned formula (II) is relative to ethylene-polar monomer copolymer 100
Mass parts, preferably more than 0.01 mass parts below 3.0 mass parts, more preferably more than 0.05 mass parts below 2.0 mass parts,
Particularly preferably more than 0.1 mass parts below 1.0 mass parts.If the content of diacrylate compounds be above-mentioned lower limit with
On, then the PID patience of gained solar module can be made better.If the in addition, content of diacrylate compounds
Below above-mentioned higher limit, then the resistance to incipient scorch of diaphragm seal can be made better.
Two propylene represented selected from two (methyl) acrylate compounds represented by above-mentioned formula (I) and by above-mentioned formula (II)
The content of at least one of ester compound compound is preferably relative to the mass parts of ethylene-polar monomer copolymer 100
More than 0.01 mass parts below 3.0 mass parts, more preferably more than 0.05 mass parts below 3.0 mass parts, more preferably
More than 0.05 mass parts below 2.0 mass parts, more preferably more than 0.1 mass parts below 2.0 mass parts, particularly preferably
More than 0.1 mass parts below 1.0 mass parts.If selected from two (methyl) acrylate compounds that are represented by above-mentioned formula (I) and
The content of at least one of the diacrylate compounds represented by above-mentioned formula (II) compound is more than above-mentioned lower limit, then
The PID patience of gained solar module can be made better.In addition, if selected from the two (first represented by above-mentioned formula (I)
Base) acrylate compounds and at least one of the diacrylate compounds compound represented by above-mentioned formula (II) content
Below above-mentioned higher limit, then the resistance to incipient scorch of diaphragm seal can be made better.
In addition, crosslinking coagent is with being selected from by two (methyl) acrylate compounds of above-mentioned formula (I) expression and by above-mentioned formula
(II) the total of at least one of diacrylate compounds represented content of compound is total to relative to ethylene-polar monomer
The mass parts of polymers 100, preferably more than 0.2 mass parts below 8.0 mass parts, 6.0 mass parts more preferably more than 0.5 mass parts
Hereinafter, more preferably more than 0.6 mass parts below 5.0 mass parts.
The other additive ＞ of ＜
, can be in the range of the purpose of the present invention not be damaged suitably containing described in detail above in the diaphragm seal of present embodiment
Each composition beyond various composition.For example, can suitably contain selected from silane coupler, ultra-violet absorber, light stabilizer,
One or two or more kinds of additives in antioxidant etc..
(silane coupler)
The content of silane coupler in the diaphragm seal of present embodiment is relative to the matter of ethylene-polar monomer copolymer 100
Part is measured, it is further excellent more preferably more than 0.1 mass parts below 3 mass parts preferably more than 0.1 mass parts below 5 mass parts
Elect as more than 0.1 mass parts below 1.5 mass parts.
If the content of silane coupler is more than above-mentioned lower limit, diaphragm seal can be made bonding with other components strong
Degree is better.On the other hand, if silane coupler is below above-mentioned higher limit, origin comes from the methoxy of silane coupler
Base, ethyoxyl hydrolysis caused by methanol, ethanol tail off, can more reliably suppress to produce bubble in diaphragm seal.
As silane coupler, can use be selected from VTES, vinyltrimethoxy silane,
Vinyl three ('beta '-methoxy Ethoxysilane), 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- glycidoxies
Hydroxypropyl methyl dimethoxysilane, 3- glycidoxypropyltrime,hoxysilanes, the second of 3- glycidoxypropyls two or three
TMOS, 3- glycidoxypropyl groups triethoxysilane, to styryl trimethoxy silane, the ethoxy of 3- aminopropyls three
Base silane, 3- TSL 8330s, N-2- (amino-ethyl) -3- amino propyl methyls dimethoxysilane, N-2-
(amino-ethyl) -3- TSL 8330s, 3- triethoxysilyls-N- (1,3- dimethyl-butylidene) third
Base amine, N- phenyl -3- TSL 8330s, 3- ureidopropyltriethoxysilanes, the second of 3- isocyanates propyl group three
TMOS, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloyloxypropyl methyl dimethoxy silicon
Alkane, 3- methacryloxypropyls, 3- methacryloyloxypropyl methyls diethoxy silane, 3- third
One or two or more kinds in alkene acryloxypropylethoxysilane trimethoxy silane etc..
Wherein, from cementability raising from the viewpoint of, preferably using selected from 3- glycidoxypropyltrime,hoxysilanes,
3- glycidoxypropyl groups triethoxysilane, APTES, 3- methacryloxypropyl front threes
TMOS, 3- methacryloxypropyls, 3- acryloxypropyls trimethoxy silane, vinyl
One or two or more kinds in triethoxysilane.
(ultra-violet absorber, light stabilizer, antioxidant)
The diaphragm seal of present embodiment, which can contain, is selected from what is be made up of ultra-violet absorber, light stabilizer and antioxidant
One or two or more kinds of additives in group.Total content of these additives is relative to ethylene-polar monomer copolymer 100
Mass parts, preferably more than 0.005 mass parts below 5 mass parts.By being set to the scope, raising can be substantially ensured that to constant temperature
The patience of constant humidity, the patience of thermal cycle, the effect of weathering stability and heat-resistant stability, further, it is possible to prevent the saturating of diaphragm seal
The reduction of bright property, cementability.Further, at least two kinds of additives in above-mentioned three kinds are preferably comprised, are particularly preferably contained
Above-mentioned three kinds of whole.
As ultra-violet absorber, can use be selected from 2- hydroxyl -4- n-octyl epoxides benzophenone, 2- hydroxyls -
4- methoxy benzophenones, 2,2- dihydroxy -4- methoxy benzophenones, 2- hydroxyl -4- methoxyl group -2- carboxyl benzophenones,
The benzophenone series ultra-violet absorbers such as 2- hydroxyl -4-N- octyloxybenzophenones；2- (2- hydroxyl -3,5- di-tert-butyl-phenyls)
The benzos such as BTA, 2- (2- hydroxy-5-methyl bases phenyl) BTA, 2- (2- hydroxyl -5- t-octyls phenyl) BTA
Triazole system ultra-violet absorber；Phenyl salicylate, salicylic acid are in the salicylate such as octyl phenyl ester system ultra-violet absorber etc.
One or two or more kinds.
As light stabilizer, can use be selected from 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. the amine compound that is obstructed, hindered piperidine system
One or two or more kinds in compound etc..
, can use be selected from three (2,4- di-t-butyl phenyl) phosphite esters, double [2,4- is double as antioxidant
(1,1- dimethyl ethyls) -6- aminomethyl phenyls] ethyl ester phosphorous acid, four (2,4- di-tert-butyl-phenyls) [1,1- biphenyl] -4,4 ' -
The phosphite ester system antioxidants such as diyl biphosphinate, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites；3-
The lactone system such as reaction product of hydroxyl -5,7- di-t-butyls-furans -2- ketone and ortho-xylene antioxidant；3,3’,3”,5,
5 ', 5 "-six tert-butyl group-a, a ', a "-(bases of methylene -2,4,6- three) three-paracresol, 1,3,5- trimethyls -2,4,6- three (3,
5- di-tert-butyl-hydroxy phenyls) benzyl benzene, pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], ten
Double [3- (3,5- di-t-butyl -4- the hydroxyls of eight alkyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, thiodiethylene
Base phenyl) propionic ester] etc. hindered phenol series antioxidant；Sulphur system antioxidant；One kind in amine system antioxidant etc. or two kinds with
On.Wherein, preferably phosphite ester system antioxidant and hindered phenol series antioxidant.
＜ diaphragm seals ＞
The thickness of diaphragm seal in present embodiment is not particularly limited, but preferably more than 0.01mm below 2mm, more excellent
Elect more than 0.2mm below 1.2mm as.If thickness is in the range of being somebody's turn to do, can suppress to be laminated in process, light surface side protection
The breakage of component, solar cell device, membrane electrode etc., also, can be obtained by ensuring sufficient light transmittance
High light generated energy.Further, the laminated into type of solar module can be carried out at low temperature, therefore preferably.
In the diaphragm seal of present embodiment, other layers can be laminated in the range of the purpose of the present invention is not damaged.Example
Such as, can have and be used to protect the layers such as positive or the back side hard conating, adhesive linkage, anti-reflection layer, gas barrier layer, stain-proofing layer.If
Classify by material, then can enumerate the layer comprising uv curing resin, the layer comprising thermosetting resin, comprising polyolefin tree
The layer of fat, the layer comprising carboxyl acid modified vistanex, the layer comprising fluorine resin, include cyclic olefin (co) polymer
Layer, layer comprising inorganic compound etc..
Shrinkage during heating on the diaphragm seal of present embodiment, the preferably heat according to JIS C2318-1997 measure
Shrinkage factor is less than 25%, more preferably less than 15%., can be more effective by the way that percent thermal shrinkage is set to below above-mentioned higher limit
Ground suppression solar cell device when making solar module misplaces in solar module, solar cell member
Part is damaged.
(manufacture method of diaphragm seal)
The manufacture method of the diaphragm seal of present embodiment is not particularly limited, and can use known various forming methods
(cast molding, extrusion sheetmolding, inflation shaping, injection moulding, compression forming, calendering formation etc.).Particularly preferably it is extruded into
Type and calendering formation.
The manufacture method of the diaphragm seal of present embodiment is not particularly limited, for example, following methods can be enumerated.First, will
Ethylene-polar monomer copolymer, crosslinking agent, crosslinking coagent, selected from two (methyl) the acrylate chemical combination represented by above-mentioned formula (I)
Thing and at least one of the diacrylate compounds compound represented by above-mentioned formula (II) and as needed other add
Agent is added to carry out dry type mixing.Then, gained mixture is supplied to extruder from hopper, it is small in one than crosslinking agent as needed
When the low temperature of half life temperature carry out melting mixing.Then, sealing is manufactured from the front end extrusion molding of extruder for sheet
Piece.Shaping can be carried out by using method known to T-shaped die extruder, calendering formation machine, inflation forming machine etc..
In addition it is also possible to make the piece without crosslinking agent by the above method, added by impregnated with method in made piece
Add crosslinking agent.In addition, in the case of comprising more than two kinds of crosslinking agent, in one hour half-life period temperature than minimum crosslinking agent
Spend low temperature and carry out melting mixing.
2. on solar module
The diaphragm seal of present embodiment is used to seal solar cell device in solar module.
As the composition of solar module, for example, be sequentially laminated with face side transparent protection member/by
Smooth surface side seal piece (smooth surface side seal layer)/solar cell device/rear side diaphragm seal (rear side sealant)/rear side
The composition of component (backboard) is protected, but is not particularly limited.
The diaphragm seal of present embodiment can be used for appointing in above-mentioned smooth surface side seal piece and above-mentioned rear side diaphragm seal
One or both.
Fig. 1 represents one of the sectional view of the solar module 10 of present embodiment.
Solar module 10 possesses：Multiple solar cell devices 13；Clip solar cell device 13 and seal
A pair of smooth surface side seal pieces 11 and rear side diaphragm seal 12；And face side transparent protection member 14 and rear side protection structure
Part (backboard) 15.
(solar cell device)
As solar cell device 13, can use the silicon systems such as monocrystalline silicon, polysilicon, amorphous silicon, gallium-arsenic,
The various solar cell devices such as the iii-vs such as copper-indium-selenium, cadmium-tellurium, II-VI group group compound semiconductor system.
In solar module 10, multiple solar cell devices 13 are via possessing the mutual of wire and solder-joint parts
Line 16 and be electrically connected in series.
(face side transparent protection member)
As face side transparent protection member 14, for example, glass plate；By acrylic resin, makrolon,
Polyester, fluorine resin etc. and the resin plate etc. formed.
(rear side protection component)
As rear side protection component (backboard) 15, for example, metal, various thermoplastic resin films etc. individually or
The piece of multilayer.For example, the metals such as tin, aluminium, stainless steel；The inorganic material such as glass；By polyester, organic/inorganic substance is deposited
Various thermoplastic resin films of the formation such as polyester, fluorine resin, polyolefin etc..
Rear side protection component 15 can be individual layer, or multilayer.
The diaphragm seal of present embodiment shows good to these face side transparent protection members 14 and rear side protection component 15
Good cementability.
(manufacture method of solar module)
The manufacture method of the solar module 10 of present embodiment is not particularly limited, for example, can enumerate following
Method.
First, by a pair of smooth surface side seal pieces of multiple solar cell devices 13 of electrical connection using interconnection line 16
11 and rear side diaphragm seal 12 clamp, it is further that these smooth surface side seal pieces 11 and rear side diaphragm seal 12 are saturating with face side
Bright protection component 14 and rear side protection component 15 clamp and make layered product.Then, layered product is heated, light surface side is close
Mounting 11 and rear side diaphragm seal 12, smooth surface side seal piece 11 and face side transparent protection member 14, rear side diaphragm seal 12
It is be bonded with rear side protection component 15.
More specifically, diaphragm seal is heated to not decomposing on the Low molecular weight contained by diaphragm seal and ethylene-polar list
Temperature as precursor copolymer melting, respectively by smooth surface side seal piece 11 and rear side diaphragm seal 12, smooth surface side seal piece
11 protect the temporary bond of component 15 with face side transparent protection member 14, rear side diaphragm seal 12 and rear side.Then heat up, enter
Row is sufficiently bonded, and further carries out the crosslinking of the ethylene-polar monomer copolymer in diaphragm seal.Bonding and the temperature of crosslinking are only
If the crosslinking rate that should be satisfied with can be obtained and do not expand such temperature, such as 100~180 can be set to
DEG C or so temperature range.
More than, embodiments of the present invention are illustrated referring to the drawings, but they are the illustrations of the present invention, can also be adopted
With various compositions other than the above.
Embodiment
Hereinafter, the present invention is illustrated based on embodiment, but the present invention is not limited to these embodiments.
The making ＞ of ＜ diaphragm seals
It is following to make on embodiment 1A~4A and comparative example 1A~3A and embodiment 1B~3B and comparative example 1B~4B
Diaphragm seal.First, according to table 1A and table 1B shown in cooperation, by vinyl-vinyl acetate copolymer (EVA), crosslinking agent, crosslinking
Prescription as shown in table 1A and table 1B of auxiliary agent, acrylate compounds, silane coupler, light stabilizer and antioxidant coordinate and
Obtain resin combination.
Using the extruder with T-shaped mould head, by the sealing that the resin combination extrusion molding of gained is about 450 μm of thickness
Piece.
In addition, the unit of the mixing ratio of each composition in table 1A and table 1B is mass parts.In addition, in table 1A and table 1B
The details of each composition is as described below.
·EVA：Vinyl-vinyl acetate copolymer (vinyl acetate containing ratio 28 mass %, MFR：15g/10 minutes)
Crosslinking agent：Tert-butyl hydroperoxide -2- ethylhexyl carbonates
Crosslinking coagent：Triallyl isocyanurate
Acrylate compounds 1A：(m+n is 2, R to propylene glycol diacrylate in formula (I)1And R3For hydrogen atom, R2
For the compound of methyl)
Acrylate compounds 2A：(m+n is 3, R to tripropylene glycol diacrylate in formula (I)1And R3For hydrogen atom, R2
For the compound of methyl)
Acrylate compounds 3A：(m+n is 4, R to polyethylene glycol #200 diacrylates in formula (I)1~R3All hydrogen
The compound of atom)
Acrylate compounds 4A：Trimethylolpropane trimethacrylate
Acrylate compounds 1B：Triethylene glycol diacrylate (compound that k is 3 in formula (II))
Acrylate compounds 2B：Polyethylene glycol #200 diacrylates (compound that k is 4 in formula (II))
Acrylate compounds 3B：TEGDMA
Acrylate compounds 4B：Trimethylolpropane trimethacrylate
Silane coupler：3- methacryloxypropyl trimethoxy silanes
Light stabilizer：Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
Antioxidant：Octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester
＜ PID performance evaluations ＞
Using the diaphragm seal obtained in embodiment and comparative example, the little module of 1 unit is made, is evaluated.Glass
The blank float glass for the Asahi Glass fabritech for cutting into 24 × 21cm has been used (at the heat with embossing thick 3.2mm
Manage glass).Solar cell device has used 156mm × 156mm unit (Gintech company systems).As backboard, bag is used
PET systems backboard containing the PET that silica has been deposited, in the part cutter incision about 2cm of backboard otch, take out single
The plus end and negative terminal of member, use vacuum laminator (NPC company systems：LM-110x160-S) with 150 DEG C of temperature of heat plate, vacuum
3 minutes time, 15 minutes pressing times are laminated.Then, the diaphragm seal and backboard stretched out from glass is cut, to glass edge
Edge assigns end face seal material, installs aluminium chassis.Then, for the cutting part from the terminal part that backboard takes out, assigning RTV has
Machine silicon makes its solidification, obtains mini module.
The plus end of the mini module and negative terminal is short-circuit, it is connected to the high-pressure side cable of power supply.This external power it is low
The cable of pressure side is connected with aluminium chassis, aluminium chassis ground connection.The module is positioned over 60 DEG C, in 85%Rh constant temperature and humidity cabinet, etc.
After temperature rising, kept in the state of application -1000V.
High voltage power supply has used pinidine PRECISION company system HARb-3R10-LF, and constant temperature and humidity cabinet has used ETAC public
Department FS-214C2 processed.
To the module for the voltage for being applied with 96 hours, the light intensity with AM (air quality, air mass) 1.5A levels is used
The xenon light source for spending distribution evaluates IV characteristics.IV evaluates the PVS-116i-S for having used Nisshinbo precision machinery company system.
Evaluation result is classified as follows.Show the result in table 1A and table 1B.
The maximum output electrical power P of IV characteristics after experimentmaxCompared with initial value
Electromotive power output is reduced to less than 5%：A
The reduction of electromotive power output is more than 5%：B
The uniformly dispersed evaluation ＞ of ＜
The diaphragm seal obtained in embodiment and comparative example is cut out 10 with A4 sizes, pack by aluminium foil laminate in line style
Low density polyethylene (LDPE) (density：0.919g/cm3MFR (according to ASTM D1238, under conditions of 190 DEG C, 2.16kg load)：
8g/10 minutes) obtained by pack piece in.Made bundling body is taken care of in 40 DEG C × 90%Rh constant temperature and humidity cabinet, mesh
Additive depending on the diaphragm seal surface after confirming 1 month oozes out state.
Evaluation result is classified as described below.Show the result in table 1A and table 1B.
Keeping after diaphragm seal surface state be,
Nothing is oozed out：A
Have and ooze out：B
The resistance to incipient scorch evaluation ＞ of ＜
To the resin combination obtained in embodiment and comparative example, resistance to incipient scorch has been carried out using Haake company systems MiniLab
The evaluation of property.The resin combination obtained in embodiment and comparative example is kneaded with 120 DEG C of design temperature, screw speed 30rpm, really
Recognize the time untill resin moment of torsion rises 0.1Nm from minimum value.
Evaluation result is classified as follows.Show the result in table 1A and table 1B.
Resin moment of torsion from minimum value rise 0.1N/m untill time be,
More than 5 minutes：A
Less than 5 minutes：B
[table 1A]
Table 1A
[table 1B]
Table 1B
The application advocates preferential based on Japanese publication Patent filed in 31 days March in 2015 2015-071504
Power and the priority based on Japanese publication Patent filed in 15 days December in 2015 2015-244502, by its disclosure
Full content be incorporated into herein.
Claims (8)
1. a kind of diaphragm seal, is the diaphragm seal for sealing solar cell device, it is included：
Ethylene-polar monomer copolymer,
Crosslinking agent,
Selected from by di vinyl aromatic compounds of group, cyanurate compound, diallyl compound, triallyl compound,
One or two or more kinds of crosslinking coagents in the group of oxime compound and maleimide compound composition, and
Selected from two (methyl) acrylate compounds represented by following formula (I)s and the diacrylate represented by following formula (II)s
At least one of compound compound,
[changing 1]
In the formula (I), R1And R3It is each independently hydrogen atom or methyl, R2For methyl, m+n is less than more than 17 integer,
[changing 2]
In the formula (II), k is less than more than 13 integer.
2. diaphragm seal according to claim 1, the ethylene-polar monomer copolymer is total to comprising ethane-acetic acid ethyenyl ester
Polymers.
3. diaphragm seal according to claim 2, vinyl acetate is derived from the vinyl-vinyl acetate copolymer
The content ratio of construction unit be below the mass % of more than 10 mass % 47.
4. according to diaphragm seal according to any one of claims 1 to 3, the R in the formula (I)1And R3It is hydrogen atom.
5. according to diaphragm seal according to any one of claims 1 to 4, the m+n in the formula (I) is 2 or 3.
6. according to diaphragm seal according to any one of claims 1 to 3, the k in the formula (II) is 3.
7. according to diaphragm seal according to any one of claims 1 to 6, selected from two (methyl) propylene represented by the formula (I)
The content of ester compound and at least one of the diacrylate compounds compound represented by the formula (II) relative to
The mass parts of ethylene-polar monomer copolymer 100 are more than 0.01 mass parts below 3.0 mass parts.
8. a kind of solar module, it possesses：
Face side transparent protection member,
Rear side protects component,
Solar cell device, and
Sealant, it is made up of the cross-linking agent of diaphragm seal according to any one of claims 1 to 7, also, by the solar energy
Cell device is sealed between the face side transparent protection member and rear side protection component.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015071504 | 2015-03-31 | ||
| JP2015-071504 | 2015-03-31 | ||
| JP2015-244502 | 2015-12-15 | ||
| JP2015244502 | 2015-12-15 | ||
| PCT/JP2016/053550 WO2016158009A1 (en) | 2015-03-31 | 2016-02-05 | Encapsulating sheet and solar cell module |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107429013A true CN107429013A (en) | 2017-12-01 |
Family
ID=57004500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680014679.7A Withdrawn CN107429013A (en) | 2015-03-31 | 2016-02-05 | Diaphragm seal and solar module |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2016158009A1 (en) |
| KR (1) | KR20170108058A (en) |
| CN (1) | CN107429013A (en) |
| WO (1) | WO2016158009A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101472853A (en) * | 2006-06-19 | 2009-07-01 | 株式会社普利司通 | Composition for forming interlayer for laminated glass, interlayer for laminated glass, and laminated glass |
| CN102666616A (en) * | 2009-11-26 | 2012-09-12 | 株式会社普利司通 | Sealing film for solar cells, and solar cells |
| CN104105773A (en) * | 2012-02-10 | 2014-10-15 | 三井化学东赛璐株式会社 | Solar cell sealing material and solar cell module |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070295388A1 (en) * | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Solar assembly with a multi-ply barrier layer and individually encapsulated solar cells or solar cell strings |
| JP4793512B2 (en) * | 2009-08-07 | 2011-10-12 | 東洋インキＳｃホールディングス株式会社 | Method for producing resin composition for solar cell encapsulant, resin composition for solar cell encapsulant, solar cell encapsulant, and solar cell module |
| CN102732160B (en) * | 2012-07-06 | 2013-12-04 | 广州鹿山新材料股份有限公司 | EVA (ethylene vinyl acetate copolymer) packaging adhesive film capable of improving light spectrum conversion efficiency of solar cell module |
-
2016
- 2016-02-05 WO PCT/JP2016/053550 patent/WO2016158009A1/en active Application Filing
- 2016-02-05 JP JP2017509344A patent/JPWO2016158009A1/en active Pending
- 2016-02-05 KR KR1020177023315A patent/KR20170108058A/en not_active Application Discontinuation
- 2016-02-05 CN CN201680014679.7A patent/CN107429013A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101472853A (en) * | 2006-06-19 | 2009-07-01 | 株式会社普利司通 | Composition for forming interlayer for laminated glass, interlayer for laminated glass, and laminated glass |
| CN102666616A (en) * | 2009-11-26 | 2012-09-12 | 株式会社普利司通 | Sealing film for solar cells, and solar cells |
| CN104105773A (en) * | 2012-02-10 | 2014-10-15 | 三井化学东赛璐株式会社 | Solar cell sealing material and solar cell module |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016158009A1 (en) | 2017-09-28 |
| WO2016158009A1 (en) | 2016-10-06 |
| KR20170108058A (en) | 2017-09-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20171201 |