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CN104334631A - 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
CN104334631A
CN104334631A CN201380026151.8A CN201380026151A CN104334631A CN 104334631 A CN104334631 A CN 104334631A CN 201380026151 A CN201380026151 A CN 201380026151A CN 104334631 A CN104334631 A CN 104334631A
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Prior art keywords
solar cell
sealing material
cell sealing
alpha
ethene
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CN104334631B (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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Photovoltaic Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

This solar cell sealing material contains, as essential components, an ethylene/alpha-olefin copolymer, an organic peroxide and an acid acceptor. It is preferable that the acid acceptor is composed of at least one substance that is selected from the group consisting of magnesium hydroxide, magnesium oxide, zinc oxide, trilead tetraoxide, calcium hydroxide, aluminum hydroxide, iron (II) hydroxide, calcium carbonate, and hydrotalcite compounds and/or fired products thereof.

Description

Solar cell sealing material and solar module
Technical field
The present invention relates to solar cell sealing material and solar module.
Background technology
In the seriousness increase process of global environmental problems, energy problem etc., as clean and do not worry that the exhausted energy generates means, solar cell receives publicity.When by the outdoor application such as roof parts of solar cell at buildings, generally use with the form of solar module.
Above-mentioned solar module, generally speaking, is manufactured by following steps.First, manufacture the crystal type solar cell device formed by polycrystal silicon, monocrystalline silicon etc. and (below, be expressed as generating element or unit.), or amorphous silicon, silicon metal etc. are formed on the substrates such as glass the very thin film of several μm and the thin film solar cell element etc. obtained.
Next; in order to obtain crystal type solar module, carry out lamination according to the order of solar module screening glass (face side transparent protection member)/solar cell sealing material/crystal type solar cell device/solar cell sealing material/solar module screening glass (rear side protection component).
On the other hand, in order to obtain film system solar module, carry out lamination according to the order of thin film solar cell element/solar cell sealing material/solar module screening glass (rear side protection component).Then, they vacuumized by utilizing and adds the laminating etc. of thermo-compressed, manufacturing solar module.The solar module of such manufacture has weathering resistance, is also suitable for the outdoor application such as roof parts at buildings.
As solar cell sealing material, vinyl-vinyl acetate copolymer (EVA) film, due to excellences such as the transparency, flexibility and cementabilities, is therefore widely used (for example, referring to patent documentation 1 ~ 4).But when the constituent material using EVA composition as solar cell sealing material, the compositions such as the acetic acid gas that worry EVA decomposes and produces bring the possibility of impact on solar cell device.
On the other hand, the solar cell sealing material resin combination (for example, referring to patent documentation 5) comprising ethene-alpha-olefin copolymer, organo-peroxide and silane coupling agent is proposed.It is said the thermotolerance of this solar cell sealing material resin combination, the transparency, flexibility and excellent in adhesion to glass substrate.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-115344 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-118073 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-15346 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2012-19179 publication
Patent documentation 5: International Publication No. 2010/114028 brochure
Summary of the invention
Invent problem to be solved
But, according to the research of the present inventor etc., although the solar cell sealing material resin combination described in known patent documentation 5 has the cementability to glass substrate, to the metal electrode of solar cell and the cementability of solder insufficient.In addition known, the cementability under fixed temperature and humidity of the solar cell sealing material resin combination described in patent documentation 5 reduces.
Therefore, it is excellent in adhesion that problem of the present invention is to provide metal electrode and solder, and, even if also can the solar cell sealing material of long term maintenance cementability under fixed temperature and humidity.
For solving the means of problem
The present inventor etc. conduct in-depth research repeatedly for the cementability of solar cell sealing material to metal electrode and solder.Found that, by in the solar cell sealing material that makes to comprise ethene-alpha-olefin copolymer and organo-peroxide further containing antacid, what can obtain metal electrode and solder is excellent in adhesion, and, even if also can the solar cell sealing material of long term maintenance cementability under fixed temperature and humidity, thus complete the present invention.
That is, according to the present invention, solar cell sealing material shown below and solar module can be provided.
[1]
A kind of solar cell sealing material, it comprises ethene-alpha-olefin copolymer, organo-peroxide and antacid.
[2]
Solar cell sealing material according to above-mentioned [1], above-mentioned antacid comprises at least a kind in the group being selected from and being made up of magnesium hydroxide, magnesium oxide, zinc oxide, tri-lead tetroxide, calcium hydroxide, aluminium hydroxide, ironic hydroxide (II), calcium carbonate and hydrotalcite compound and/or its burned material.
[3]
Solar cell sealing material according to above-mentioned [1] or [2], the content of the above-mentioned antacid in this solar cell sealing material is 0.1 ~ 3.0 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[4]
Solar cell sealing material according to any one of above-mentioned [1] ~ [3], above-mentioned ethene-alpha-olefin copolymer meets following important document a1) ~ a4),
A1) derive from the Component units of ethene containing proportional be 80 ~ 90mol%, derive from the Component units of the alpha-olefin of carbonatoms 3 ~ 20 containing proportional be 10 ~ 20mol%,
A2) according to ASTM D1238,190 DEG C, to measure the MFR obtained under the condition of 2.16kg loading be 10 ~ 50g/10 minute,
A3) measuring according to ASTM D1505 the density obtained is 0.865 ~ 0.884g/cm 3,
A4) measuring according to ASTM D2240 the Xiao A hardness obtained is 60 ~ 85.
[5]
Solar cell sealing material according to above-mentioned [4], according to ASTM D1238,190 DEG C, the MFR that measures the above-mentioned ethene-alpha-olefin copolymer obtained under the condition of 2.16kg loading is 10 ~ 27g/10 minute.
[6]
Solar cell sealing material according to any one of above-mentioned [1] ~ [5], the median diameter in the volume reference size-grade distribution obtained by laser diffraction and scattering formula particle size distribution method of above-mentioned antacid is less than 1.0 μm.
[7]
Solar cell sealing material according to any one of above-mentioned [1] ~ [6], above-mentioned antacid is the hydrotalcite compound shown in following general formula (A) and/or its burned material,
M 2+ 1-a·M 3+ a(OH) 2·An n- a/n·mH 2O (A)
(0.2≤a≤0.35,0≤m≤5, M 2+: be selected from Mg 2+, Zn 2+, Ni 2+, Ca 2+in at least a kind of divalent metal ion, M 3+: be selected from Al 3+, Fe 3+in at least a kind of 3 valence metal ion, An:n valency negatively charged ion)
[8]
Solar cell sealing material according to above-mentioned [7], the average plate face diameter of above-mentioned hydrotalcite compound is 0.02 ~ 0.9 μm.
[9]
Solar cell sealing material according to any one of above-mentioned [1] ~ [8], 1 minute half life temperature of above-mentioned organo-peroxide is 100 ~ 170 DEG C,
The content of the above-mentioned organo-peroxide in this solar cell sealing material is 0.1 ~ 3 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[10]
Solar cell sealing material according to any one of above-mentioned [1] ~ [9], it comprises silane coupling agent further,
The content of the silane coupling agent in this solar cell sealing material is 0.1 ~ 5 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[11]
Solar cell sealing material according to any one of above-mentioned [1] ~ [10], it comprises hindered phenol system stablizer further,
The content of the above-mentioned hindered phenol system stablizer in this solar cell sealing material is 0.005 ~ 0.1 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[12]
Solar cell sealing material according to any one of above-mentioned [1] ~ [11], it comprises hindered amine system photostabilizer further,
The content of the above-mentioned hindered amine system photostabilizer in this solar cell sealing material is 0.01 ~ 2.0 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[13]
Solar cell sealing material according to any one of above-mentioned [1] ~ [12], it comprises phosphorus system stablizer further,
The content of the above-mentioned phosphorus system stablizer in this solar cell sealing material is 0.005 ~ 0.5 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[14]
Solar cell sealing material according to any one of above-mentioned [1] ~ [13], it comprises UV light absorber further,
The content of the above-mentioned UV light absorber in this solar cell sealing material is 0.005 ~ 5 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[15]
Solar cell sealing material according to any one of above-mentioned [1] ~ [14], it comprises crosslinking coagent further,
The content of the above-mentioned crosslinking coagent in this solar cell sealing material is 0.05 ~ 5 weight part relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part.
[16]
Solar cell sealing material according to any one of above-mentioned [1] ~ [15], it is by by after above-mentioned ethene-alpha-olefin copolymer, above-mentioned organo-peroxide and above-mentioned antacid melting mixing, and sheet ground extrusion moulding obtains.
[17]
Solar cell sealing material according to any one of above-mentioned [1] ~ [16], it is sheet.
[18]
A kind of solar module, it possesses:
Face side transparent protection member,
Rear side protection component,
Solar cell device, and
Sealing ply, described sealing ply makes the solar cell sealing material described in any one of above-mentioned [1] ~ [17] crosslinked and formed, and above-mentioned solar cell device is sealed in above-mentioned face side transparent protection member and above-mentioned rear side is protected between component.
The effect of invention
According to the present invention, what can provide metal electrode and solder is excellent in adhesion, and, even if also can the solar cell sealing material of long term maintenance cementability under fixed temperature and humidity.
In addition, according to the present invention, by using such solar cell sealing material, except above-mentioned excellent, even if temperature rises when using solar module, sealing material also can be avoided to be out of shape such problem.And, also can not damage the outward appearance of solar cell, may be provided in this etc. the solar module of economy excellence.
Accompanying drawing explanation
Above-mentioned purpose and other objects, features and advantages are come clear and definite further by the preferred implementation of the following stated and appended the following drawings thereof.
Fig. 1 is the sectional view of the embodiment schematically showing solar module of the present invention.
Fig. 2 is the orthographic plan schematically showing the sensitive surface of solar cell device and a configuration example at the back side.
Embodiment
Below, accompanying drawing is used to be described embodiments of the present invention.In addition, in whole accompanying drawing, same symbol is enclosed to same integrant, suitably omits the description.In addition, about " ~ ", if do not specialized, then represent above to following.
1. about solar cell sealing material
Solar cell sealing material of the present invention comprises ethene-alpha-olefin copolymer, organo-peroxide and antacid as neccessary composition.According to the present invention, by in the solar cell sealing material that makes to comprise ethene-alpha-olefin copolymer and organo-peroxide further containing antacid, what can obtain metal electrode and solder is excellent in adhesion, further, even if also can the solar cell sealing material of long term maintenance cementability under fixed temperature and humidity.The reason that can obtain such effect is not necessarily clear, but is presumed as follows.
First, solar module is generally by obtaining solar cell device and metal electrode solder bonds.
Here, in order to the wettability of the solder making the junction surface of metal electrode and solar cell device and metal electrode junction surface each other improves, usually at surface of metal electrode coating rosin series solder flux or water soluble flux.About the lipid acid that this flux constituent comprises, due to such as 85 DEG C, penetrate into the moisture in solar cell sealing material under the fixed temperature and humidity of 85%rh thus acid produced.
According to the research of the present inventor etc., specify that the above-mentioned acid by being produced by flux constituent, the silane coupling agent in solar cell sealing material and the combination of metal electrode are cut off, and consequently, cementability reduces.
Solar cell sealing material of the present invention, owing to comprising antacid, therefore can catch the above-mentioned acid of generation by antacid.Consequently, the cut-out of the combination that can suppress silane coupling agent and the metal electrode caused by acid can be thought.Be speculated as the above-mentioned reasons, solar cell sealing material of the present invention, make to improve the cementability of metal line and solder, even if simultaneously also can long term maintenance cementability under fixed temperature and humidity.
In addition, in the solar cell sealing material described in patent documentation 1 ~ 4, although also with the addition of antacid, this antacid is added to catch the acetic acid produced by vinyl-vinyl acetate copolymer (EVA).Therefore, different from the technical meaning of antacid of the present invention.
(ethene-alpha-olefin copolymer)
The solar cell sealing material of present embodiment, comprising following ethene-alpha-olefin copolymer is one of optimal way.
The solar cell sealing material of present embodiment ethene-alpha-olefin copolymer used is by carrying out copolymerization to obtain by the alpha-olefin of ethene and carbonatoms 3 ~ 20.As alpha-olefin, usually, can be used alone the alpha-olefin of a kind of carbonatoms 3 ~ 20 or combinationally use two or more.As the alpha-olefin of carbonatoms 3 ~ 20, the alpha-olefin of straight-chain or branched can be enumerated, such as, propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butylene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene etc.Wherein preferably carbonatoms is the alpha-olefin of less than 10, particularly preferably is the alpha-olefin that carbonatoms is 3 ~ 8.Consider from the easiness obtained, be preferably propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and 1-octene.In addition, ethene-alpha-olefin copolymer can be random copolymers, can be also segmented copolymer, but from the viewpoint of flexibility, is preferably random copolymers.
In addition, the ethene-alpha-olefin copolymer that the solar cell sealing material of present embodiment is used can be the multipolymer formed by the alpha-olefin of ethene, carbonatoms 3 ~ 20 and unconjugated polyene.Alpha-olefin as described above, as unconjugated polyene, can enumerate 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornylene (VNB), Dicyclopentadiene (DCPD) (DCPD) etc.These unconjugated polyenes can be used alone a kind, or two or more combinationally uses.
The ethene-alpha-olefin copolymer that the solar cell sealing material of present embodiment is used can be used together aromatic ethenyl compound, such as, vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, neighbour, p-dimethyl styrene, methoxy styrene, vinyl benzoic acid, vinylbenzoate, vinyl benzyl yl acetate, hydroxy styrenes, to the styrenic such as chloro-styrene, Vinylstyrene; 3-phenylpropen, 4-phenylpropen, alpha-methyl styrene, carbonatoms are that the cyclic olefin of 3 ~ 20 is as cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene etc.
The ethene-alpha-olefin copolymer of present embodiment preferably meets following important document a1 ~ a4 further.
(important document a1)
What ethene-alpha-olefin copolymer comprised the derive from Component units of ethene be preferably 80 ~ 90mol% containing proportional, be more preferably 80 ~ 88mol%, more preferably 82 ~ 88mol%, be particularly preferably 82 ~ 87mol%.What ethene-alpha-olefin copolymer comprised derives from the Component units of the alpha-olefin of carbonatoms 3 ~ 20 (below, also be designated as " alpha-olefin unit ") containing proportional be preferably 10 ~ 20mol%, be more preferably 12 ~ 20mol%, more preferably 12 ~ 18mol%, is particularly preferably 13 ~ 18mol%.
If the alpha-olefin unit that ethene-alpha-olefin copolymer comprises containing proportional for more than 10mol%, then can obtain the high transparency.In addition, easily can carry out the extrusion moulding under low temperature, such as, can realize the extrusion moulding of less than 130 DEG C.Therefore, when refining in ethene-alpha-olefin copolymer into organo-peroxide, the carrying out of the crosslinking reaction in forcing machine also can be suppressed, the deteriorated appearance that can prevent from the sheet of solar cell sealing material from producing gelatinous foreign matter causing sheet.In addition, due to the flexibility of appropriateness can be obtained, therefore can prevent from, when solar module laminated into type, the cracking of solar cell device, the defect etc. of membrane electrode occur.
If the alpha-olefin unit that ethene-alpha-olefin copolymer comprises containing proportional for below 20mol%, then the crystallization velocity of ethene-alpha-olefin copolymer becomes appropriateness, therefore the sheet extruded from forcing machine can not be clamminess, stripping on cooling roller is easy, effectively can obtain the sheet of the solar cell sealing material of sheet.In addition, because sheet is not clamminess, therefore can prevent adhesion, the stretching out property of sheet becomes good.In addition, the reduction of thermotolerance can also be prevented.
(important document a2)
According to ASTM D1238,190 DEG C, the melt flow rate (MFR) (MFR) that measures the ethene-alpha-olefin copolymer obtained under the condition of 2.16kg loading is generally 0.1 ~ 50g/10 minute, be preferably 2 ~ 50g/10 minute, be more preferably 10 ~ 50g/10 minute, more preferably 10 ~ 40g/10 minute, be particularly preferably 12 ~ 27g/10 minute, most preferably be 15 ~ 25g/10 minute.The MFR of ethene-alpha-olefin copolymer can by adjusting polyreaction described later time polymerization temperature, polymerization pressure and polymerization system in ethene and the monomer concentration of alpha-olefin and the molar ratio etc. of hydrogen concentration adjust.
(calendering formation)
If MFR is more than 0.1g/10 minute and is less than 10g/10 minute, then can manufacture sheet by calendering formation.If MFR is more than 0.1g/10 minute and is less than 10g/10 minute, the mobility then comprising the resin combination of ethene-alpha-olefin copolymer is low, therefore preferred in the pollution that can prevent the laminater caused by the molten resin oozed out when sheet and solar cell device lamination.
(extrusion moulding)
In addition, if MFR is more than 2g/10 minute, preferred MFR is more than 10g/10 minute, then the mobility comprising the resin combination of ethene-alpha-olefin copolymer improves, and productivity during sheet extrusion moulding can be made to improve.
If MFR is less than 50g/10 minute, then molecule quantitative change is large, therefore can suppress the attachment of the roll surface to cooling roller etc., does not therefore need to peel off, can be shaped to the sheet of uniform thickness.In addition, owing to being formed, there is the resin combination of " hardness (stiff) ", therefore can the sheet of easily shaping more than 0.1mm.In addition, because crosslinking feature during solar module laminated into type improves, it therefore can be made to be cross-linked fully, suppress the reduction of thermotolerance.
If MFR is less than 27g/10 minute, then drawdown when sheet can be suppressed further shaping, can the wide sheet of forming width, and crosslinking feature and thermotolerance improve further, can obtain the best solar cell sealing material sheet.
In addition, when not carrying out the crosslinking Treatment of resin combination in the lamination of solar module described later, the impact melt extruding the decomposition of organo-peroxide in operation is little, therefore MFR also can be used for more than 0.1g/10 minute and be less than 10g/10 minute, be preferably more than 0.5g/10 minute and be less than the resin combination of 8.5g/10 minute, obtaining sheet by extrusion moulding.When the organo-peroxide content of resin combination is below 0.15 weight part, also MFR can be used for more than 0.1g/10 minute and be less than the resin combination of 10g/10 minute, carry out silane-modified process or micro-crosslinking Treatment, manufacture sheet at the mold temperature of 170 ~ 250 DEG C by extrusion moulding simultaneously.If MFR is within the scope of this, be then preferred in the pollution that can prevent the laminater caused by the molten resin oozed out when sheet and solar cell device lamination.
(important document a3)
The density measuring the ethene-alpha-olefin copolymer obtained according to ASTM D1505 is preferably 0.865 ~ 0.884g/cm 3, be more preferably 0.866 ~ 0.883g/cm 3, more preferably 0.866 ~ 0.880g/cm 3, be particularly preferably 0.867 ~ 0.880g/cm 3.The density of ethene-alpha-olefin copolymer, can adjusting containing the proportional proportional balance that contains with alpha-olefin unit by ethylene unit.If that is, improve ethylene unit containing proportional, then crystallinity uprises, and can obtain the ethene-alpha-olefin copolymer that density is high.On the other hand, if containing of reduction ethylene unit is proportional, then crystallinity step-down, can obtain low density ethene-alpha-olefin copolymer.
If the density of ethene-alpha-olefin copolymer is 0.884g/cm 3below, then crystallinity step-down, can improve the transparency.In addition, the extrusion moulding transfiguration under low temperature is easy, such as, can carry out extrusion moulding below 130 DEG C.Therefore, even if refine in ethene-alpha-olefin copolymer into organo-peroxide, also can prevent the carrying out of the crosslinking reaction in forcing machine, the sheet of solar cell sealing material can be suppressed to produce gelatinous foreign matter, suppress the deterioration of the outward appearance of sheet.In addition, because flexibility is high, therefore can prevent from occurring as the cracking of the unit of solar cell device, the defect etc. of membrane electrode when solar module laminated into type.
On the other hand, if the density of ethene-alpha-olefin copolymer is 0.865g/cm 3above, then can accelerate the crystallization velocity of ethene-alpha-olefin copolymer, the sheet therefore extruded from forcing machine is not easily clamminess, and the stripping transfiguration on cooling roller is easy, easily can obtain the sheet of solar cell sealing material.In addition, be not easily clamminess because sheet becomes, therefore can suppress the generation of adhesion, the stretching out property of sheet is improved.In addition, owing to being cross-linked fully, the reduction of thermotolerance can therefore be suppressed.
(important document a4)
The Xiao A hardness measuring the ethene-alpha-olefin copolymer obtained according to ASTM D2240 is preferably 60 ~ 85, is more preferably 62 ~ 83, and more preferably 62 ~ 80, be particularly preferably 65 ~ 80.The Xiao A hardness of ethene-alpha-olefin copolymer can adjusting in above-mentioned numerical range containing proportional, density domination by the ethylene unit by ethene-alpha-olefin copolymer.That is, the Xiao A hardness containing proportional height, ethene-alpha-olefin copolymer that density is high of ethylene unit uprises.On the other hand, the Xiao A hardness step-down containing proportional low, low density ethene-alpha-olefin copolymer of ethylene unit.
If Xiao A hardness is more than 60, then ethene-alpha-olefin copolymer becomes and is not easily clamminess, and can suppress adhesion.In addition, when solar cell sealing material is processed as sheet, the stretching out property of sheet also can be made to improve, the reduction of thermotolerance can also be suppressed.
On the other hand, if Xiao A hardness is less than 85, then crystallinity step-down, can improve the transparency.In addition, because flexibility is high, therefore can prevent when solar module laminated into type as the cracking of the unit of solar cell device, the breakage etc. of membrane electrode.
In addition, the solar cell sealing material of present embodiment, meeting following important document further is also preferred mode.
(melting peak)
Ethene-alpha-olefin copolymer, measure based on means of differential scanning calorimetry the scope that the melting peak of (DSC) is preferably present in 30 ~ 90 DEG C, be more preferably present in the scope of 33 ~ 90 DEG C, be particularly preferably present in the scope of 33 ~ 88 DEG C.If melting peak is less than 90 DEG C, then degree of crystallinity step-down, the flexibility of the solar cell sealing material of gained improves, and therefore can prevent the cracking of generating unit, the defect of membrane electrode when solar module laminated into type.On the other hand, if melting peak is more than 30 DEG C, then moderately can improve the flexibility of resin combination, therefore easily can obtain solar cell sealing material sheet by extrusion moulding.In addition, can prevent by the adhesion caused of being clamminess of sheet, suppress the deterioration of the stretching out property of sheet.
(volume intrinsic resistance)
The solar cell sealing material of present embodiment, according to JIS K6911, measures the volume intrinsic resistance obtained be preferably 1.0 × 10 with temperature 100 DEG C, applying voltage 500V 13~ 1.0 × 10 18Ω cm.The solar cell sealing material that volume intrinsic resistance is large has the tendency having and suppress PID phenomenon that such characteristic occurs.In addition, irradiate in the time-bands of sunlight, for solar module in the past, module temperature becomes such as more than 70 DEG C sometimes, therefore from the viewpoint of long-term reliability, compared with the volume intrinsic resistance under the normal temperature in the past reported (23 DEG C), more require the volume intrinsic resistance under hot conditions, the volume intrinsic resistance of temperature 100 DEG C becomes important.
According to JIS K6911, with temperature 100 DEG C, apply voltage 500V and measures the volume intrinsic resistance that obtains (below, also referred to as " volume intrinsic resistance ".) be more preferably 1.0 × 10 14~ 1.0 × 10 18Ω cm, more preferably 5.0 × 10 14~ 1.0 × 10 18Ω cm, is particularly preferably 1.0 × 10 15~ 1.0 × 10 18Ω cm.If fruit volume intrinsic resistance is 1.0 × 10 13more than Ω cm, then 85 DEG C, also can suppress the generation of about 1 day PID phenomenon in a short time in constant temperature and humid test under 85%rh.If fruit volume intrinsic resistance is 1.0 × 10 18below Ω cm, then sheet not easily produces electrostatic, therefore can the absorption of preventing pollution thing, can suppress to be mixed into pollutent in solar module and the reduction causing generating efficiency, long-term reliability.
In addition, if fruit volume intrinsic resistance is 5.0 × 10 14more than Ω cm, then 85 DEG C, have the tendency that can make the further long life of the generation of PID phenomenon in constant temperature and humid test under 85%rh, thus preferably.
Volume intrinsic resistance is after being shaped to sealing material sheet, crosslinked and measure after being processed into smooth sheet with vacuum laminator, thermocompressor, crosslinked stove etc.In addition, the sheet in module laminate body measures after other layer of removing.
(content of aluminium element)
The content (level of residue) of the aluminium element (following, to be also designated as " Al ") that ethene-alpha-olefin copolymer comprises is preferably 10 ~ 500ppm, is more preferably 20 ~ 400ppm, more preferably 20 ~ 300ppm.Al content depend on add in the polymerization process of ethene-alpha-olefin copolymer organoalurrunoxy compound, organo-aluminium compound concentration.
When Al content is more than 10ppm, the concentration of the degree that the organoalurrunoxy compound added in the polymerization process of ethene-alpha-olefin copolymer, organo-aluminium compound can fully can show with the activity of Metallocenic compound is added, and does not therefore need to add react with Metallocenic compound and form the compound of ion pair.When adding the compound of this formation ion pair, sometimes the compound of this formation ion pair remains in ethene-alpha-olefin copolymer, thus cause the reduction of electrical specification (having the tendency that the electrical specification under such as waiting high temperature at 100 DEG C reduces), but such phenomenon can be prevented.In addition, in order to reduce Al content, deliming process is carried out in needs acid, alkali, acid residual in rewarding ethene-alpha-olefin copolymer, alkali cause the tendency of the corrosion of electrode, in order to implement deliming process, the cost of ethene-alpha-olefin copolymer also uprises, but does not need such deliming process.
In addition, if Al content is below 500ppm, then can prevent the carrying out of the crosslinking reaction in forcing machine, therefore can prevent the sheet of solar cell sealing material from producing gel foreign matter, prevent the deteriorated appearance of sheet.
The method of the aluminium element that, ethene-alpha-olefin copolymer as described above as control comprises, such as, by the polymerization activity of the Metallocenic compound of the manufacturing condition of concentration in manufacturing process of (II-1) organoalurrunoxy compound described in the manufacture method that adjusts ethene-alpha-olefin copolymer described later and (II-2) organo-aluminium compound or ethene-alpha-olefin copolymer, the aluminium element that ethene-alpha-olefin copolymer comprises can be controlled.
(manufacture method of ethene-alpha-olefin copolymer)
Ethene-alpha-olefin copolymer can manufacture as catalyzer by using Ziegler compound, vanadium compound, Metallocenic compound etc.Various Metallocenic compounds shown below are wherein preferably used to manufacture as catalyzer.As Metallocenic compound, such as, the Metallocenic compound that Japanese Unexamined Patent Publication 2006-077261 publication, Japanese Unexamined Patent Publication 2008-231265 publication, Japanese Unexamined Patent Publication 2005-314680 publication etc. are described can be used.But, also can use the Metallocenic compound with the Metallocenic compound different structure described in these patent documentations, also can combinationally use more than two kinds Metallocenic compounds.
As the polyreaction using Metallocenic compound, form such as shown below can be enumerated as suitable examples.
Be selected from and react with above-mentioned Metallocenic compound (I) by (II-1) organoalurrunoxy compound, (II-2) and under forming the existence of the catalyst for olefines polymerizing of at least one compound (also referred to as promotor) in the group that the compound of ion pair and (II-3) organo-aluminium compound form comprising known Metallocenic compound and (II), supply ethene and more than one monomers be selected from alpha-olefin etc.
React with above-mentioned Metallocenic compound (I) as (II-1) organoalurrunoxy compound, (II-2) and form compound and (II-3) organo-aluminium compound of ion pair, such as, the Metallocenic compound that Japanese Unexamined Patent Publication 2006-077261 publication, Japanese Unexamined Patent Publication 2008-231265 publication and Japanese Unexamined Patent Publication 2005-314680 publication etc. are described can also be used.But, also can use the Metallocenic compound with the Metallocenic compound different structure described in these patent documentations.These compounds separately or can contact in advance and put in polymerization atmosphere.In addition, such as also can support in described Inorganic particulate oxide carriers such as Japanese Unexamined Patent Publication 2005-314680 publications and use.
In addition, the compound forming ion pair preferably by not using in fact above-mentioned (II-2) and above-mentioned Metallocenic compound (I) to react manufactures, and can obtain the ethene-alpha-olefin copolymer of excellent electrical characteristic.
The polymerization of ethene-alpha-olefin copolymer can be undertaken by any one in the liquid polymerizations such as known gaseous polymerization, slurry polymerization process and solution polymerization process.Carry out preferably by liquid polymerizations such as solution polymerization process.At use Metallocenic compound as described above, when carrying out the copolymerization of the alpha-olefin of ethene and carbonatoms 3 ~ 20 and manufacture ethene-alpha-olefin copolymer, the Metallocenic compound of (I) is generally 10 with every 1 liter of reaction volume -9~ 10 -1mole, be preferably 10 -8~ 10 -2mole such amount uses.
Compound (II-1) is generally 1 ~ 10000 with the mol ratio [(II-1)/M] of the whole transition metal atoms (M) in compound (II-1) and compound (I), and 10 ~ 5000 such amounts that are preferably use.Compound (II-2) is to be generally 0.5 ~ 50 with the mol ratio [(II-2)/M] of the whole transition metal (M) in compound (I), and 1 ~ 20 such amount that is preferably uses.Compound (II-3) is generally 0 ~ 5 mmole with every 1 liter of polymerization volume, and the amount being preferably about 0 ~ 2 mmole such uses.
In solution polymerization process, under the existence of Metallocenic compound as described above, by carrying out the copolymerization of the alpha-olefin of ethene and carbonatoms 3 ~ 20, co-monomer content can be manufactured efficiently high, composition narrowly distributing, the ethene-alpha-olefin copolymer of narrow molecular weight distribution.Here, the mol ratio that adds of the alpha-olefin of ethene and carbonatoms 3 ~ 20 is generally ethene: alpha-olefin=10:90 ~ 99.9:0.1, be preferably ethene: alpha-olefin=30:70 ~ 99.9:0.1, more preferably ethene: alpha-olefin=50:50 ~ 99.9:0.1.
So-called " solution polymerization process " is the general name that the state being dissolved with polymkeric substance in nonactive hydrocarbon solvent described later carries out the method for being polymerized.Polymerization temperature in solution polymerization process is generally 0 ~ 200 DEG C, is preferably 20 ~ 190 DEG C, more preferably 40 ~ 180 DEG C.In solution polymerization process, when polymerization temperature is discontented with 0 DEG C, its polymerization activity reduces terrifically, and the heat extraction of heat of polymerization also becomes difficulty, impracticable in productivity.In addition, if polymerization temperature is more than 200 DEG C, then polymerization activity reduces terrifically, therefore impracticable in productivity.
Polymerization pressure is generally normal pressure ~ 10MPa gauge pressure, under being preferably the condition of normal pressure ~ 8MPa gauge pressure.Copolymerization can be undertaken by the either method in intermittent type, semi continuous, continous way.Reaction times is (when copolyreaction is implemented by continuous processing, for average retention time) different from the difference of the condition such as catalyst concn, polymerization temperature, suitably can select, but be generally 1 minute ~ 3 hours, be preferably 10 minutes ~ 2.5 hours.In addition, also can be divided into different more than 2 sections of reaction conditions to be polymerized.The molecular weight of the ethene-alpha-olefin copolymer of gained also can by making the hydrogen concentration in polymerization system, polymerization temperature variations to regulate.In addition, the amount also can passing through used compound (II) regulates.When adding hydrogen, about its amount, the ethene-alpha-olefin copolymer that every 1kg generates is about 0.001 ~ 5,000NL is suitable.In addition, the vinyl and the vinylidene that are present in the molecular end of the ethene-alpha-olefin copolymer of gained by improving polymerization temperature, can be done one's utmost minimizing and adding hydrogen amount to adjust.
The solvent used in solution polymerization process is generally nonactive hydrocarbon solvent, and the boiling point be preferably under normal pressure is the stable hydrocarbon of 50 DEG C ~ 200 DEG C.Specifically, the aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene can be enumerated; The clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane.In addition, the halohydrocarbon such as benzene,toluene,xylene etc. are aromatic hydrocarbon based, ethylene chloride, chlorobenzene, methylene dichloride also fall into the category of " nonactive hydrocarbon solvent ", do not limit it and use.
As mentioned above, in solution polymerization process, not only can use the in the past conventional organoalurrunoxy compound being dissolved in aromatic hydrocarbons, and the modified methylaluminoxane as MMAO being dissolved in aliphatic hydrocarbon, clicyclic hydrocarbon can be used.Consequently, if adopt aliphatic hydrocarbon, clicyclic hydrocarbon as the solvent of solution polymerization, then the possibility of aromatic hydrocarbons is mixed in the ethene-alpha-olefin copolymer can almost get rid of completely in polymerization system, generating.That is, solution polymerization process also has and can alleviate carrying capacity of environment, can minimize such feature by the impact of HUMAN HEALTH.In addition, in order to suppress the uneven of physics value, the ethene-alpha-olefin copolymer therefore obtained preferably by polyreaction and other composition added as required are melted by arbitrary method, implement mixing, granulation etc.
(organo-peroxide)
The solar cell sealing material of present embodiment comprises organo-peroxide.Radical initiator during crosslinking reaction when the radical initiator during graft modification of organo-peroxide as silane coupling agent and ethene-alpha-olefin copolymer and solar module laminated into type as ethene-alpha-olefin copolymer and using.By to ethene-alpha-olefin copolymer graft modification silane coupling agent, can obtain and protect with face side transparent protection member, rear side the solar module that the cementability of component, unit, electrode is good.In addition, by cross-linked ethylene-alpha-olefin copolymer, thermotolerance, solar module excellent in adhesion can be obtained.
As long as the organo-peroxide of preferred use can to the organo-peroxide of ethene-alpha-olefin copolymer graft modification silane coupling agent or cross-linked ethylene-alpha-olefin copolymer, be not particularly limited, but the balance of the rate of crosslinking during productivity from extrudate piece is shaping and solar module laminated into type is considered, 1 minute half life temperature of organo-peroxide is preferably 100 ~ 170 DEG C.If half life temperature was more than 100 DEG C in 1 of organo-peroxide minute, then the solar cell sealing sheet obtained by resin combination when extrudate piece is shaping becomes and not easily produces gel, therefore can suppress the rising of the torque of forcing machine and make sheet easily shaping.In addition, can suppress concavo-convex in the generation of the surface of sheet due to the jello produced in forcing machine, therefore can prevent deteriorated appearance.In addition, when applying voltage, can prevent sheet inside from ftractureing, therefore can prevent the reduction of breakdown voltage.In addition, the reduction of water vapour permeability can also be prevented.In addition, owing to can suppress to produce concavo-convex on sheet surface, therefore when the lamination process of solar module, protect the adaptation of component to become good with face side transparent protection member, unit, electrode, rear side, cementability also improves.If extrusion temperature shaping for extrudate piece is reduced to less than 90 DEG C, although then can be shaping, productivity significantly reduces.If half life temperature was less than 170 DEG C in 1 of organo-peroxide minute, then the reduction of rate of crosslinking when can suppress solar module laminated into type, therefore can prevent the productive reduction of solar module.In addition, the thermotolerance of solar cell sealing material, the reduction of cementability can also be prevented.
As organo-peroxide, known organo-peroxide can be used.As the preferred concrete example of the organo-peroxide of 1 minute half life temperature in the scope of 100 ~ 170 DEG C, dilauroyl peroxide can be enumerated, 1，1，3，3-tetra-methylbutyl peroxy-2-ethylhexanoate, diperoxy benzoyl, t-amyl peroxy-2-ethylhexanoate, tert-butyl hydroperoxide-2-ethylhexanoate, tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide maleic acid ester, 1,1-bis-(t-amyl peroxy)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(t-amyl peroxy) hexanaphthene, the different pelargonate of t-amyl peroxy, t-amyl peroxy n-caprylic acid ester, 1,1-bis-(tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane, 1,1-bis-(tert-butyl hydroperoxide) hexanaphthene, t-butylperoxyisopropyl carbonic ether, tert-butyl hydroperoxide-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-bis-(benzoyl peroxidation) hexane, tert-pentyl-peroxide benzoate, tert-butyl hydroperoxide acetic ester, the different pelargonate of tert-butyl hydroperoxide, 2,2-bis-(tert-butyl hydroperoxide) butane, tert butyl peroxy benzoate etc.Be preferably dilauroyl peroxide, t-butylperoxyisopropyl carbonic ether, tert-butyl hydroperoxide acetic ester, the different pelargonate of tert-butyl hydroperoxide, tert-butyl hydroperoxide-2-ethylhexyl carbonate, tert butyl peroxy benzoate etc.Above-mentioned organo-peroxide can be used alone one, also can more than two kinds used in combination.
The content of the organo-peroxide in solar cell sealing material, relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part, is preferably 0.1 ~ 3.0 weight part, is more preferably 0.2 ~ 3.0 weight part, is particularly preferably 0.2 ~ 2.5 weight part.
If the content of organo-peroxide is more than 0.1 weight part, then can suppress the reduction of the crosslinking feature such as crosslinking degree, rate of crosslinking of solar cell sealing material, make silane coupling agent good to the graft reaction of the main chain of vinyl copolymer, suppress the reduction of thermotolerance, cementability.
If the content of organo-peroxide is below 3.0 weight parts, then the solar cell sealing sheet obtained by resin combination when extrudate piece is shaping does not produce gel, can suppress the torque of forcing machine, and the shaping transfiguration of sheet is easy.Sheet also owing to not producing jello in forcing machine, and therefore the surface of sheet does not have concavo-convex, and outward appearance is good.In addition, owing to not having gel, even if therefore apply voltage, the cracking caused by the jello of sheet inside does not occur yet, and therefore puncture of insulation resistance is good.In addition, water vapour permeability is also good.In addition, owing to not having concavo-convex on sheet surface, therefore when the lamination process of solar module, protect the cementability of component also good with face side transparent protection member, unit, electrode, rear side.
(antacid)
The solar cell sealing material of present embodiment comprises antacid.By comprising antacid, can make to improve, even if also can long term maintenance cementability under fixed temperature and humidity the cementability of metal line and solder.
The content of the antacid in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin copolymer 100 weight part, be preferably 0.1 ~ 3.0 weight part, be more preferably 0.1 ~ 2.8 weight part, be particularly preferably 0.2 ~ 2.5 weight part, most preferably be 0.2 ~ 1.0 weight part.
If the content of antacid is more than above-mentioned lower value, then can obtain by antacid bring fully by acid energy.If the content of antacid is below above-mentioned higher limit, then can maintain the transparency of solar cell sealing material, can be good with the balance of the transparency by acidity.
In addition, such as, when manufacturing the such high density of masterbatch and coordinating the solar cell sealing material resin combination of product, 5 ~ 50 weight parts are preferably used.Use masterbatch to manufacture solar cell sealing material, consider it is preferred from the dispersion of antacid, operating aspect.
Median diameter in the volume reference size-grade distribution obtained by laser diffraction and scattering formula particle size distribution method of the antacid that the solar cell sealing material of present embodiment comprises, be preferably 0.1 ~ 1.0 μm, more preferably 0.1 ~ 0.9 μm, be particularly preferably 0.1 ~ 0.5 μm.
About solar cell sealing material, incident in large quantities in order to make the incident light of unit for solar cell, preferably there is high transparent, when being configured in sensitive surface side, especially requiring that there is the high transparency.Therefore, improve to make the high transparent of solar cell sealing material, high power generation performance is guaranteed chronically from the generating beginning initial stage, and obtain the height brought by antacid and be subject to acid energy, the median diameter of the antacid making sensitive surface side solar cell sealing material comprise is effective especially in above-mentioned scope.
By making the median diameter of above-mentioned antacid be below above-mentioned higher limit, amass owing to having high light, therefore can obtain the height that brought by antacid by acid can, and above-mentioned antacid high dispersive can be made and guarantee the high transparent of solar cell sealing material.In addition, by making the median diameter of above-mentioned antacid be more than above-mentioned lower value, the aggegation of above-mentioned antacid can be suppressed, making above-mentioned antacid high dispersive in the solar cell sealing material of above-mentioned sensitive surface side.
In addition, in the present embodiment, the median diameter of antacid can measure by such as using laser diffraction formula particle size distribution device.
In the present embodiment, the composition of the antacid contained by the solar cell sealing material of above-mentioned sensitive surface side, as long as the composition with absorption and/or antacid function, is then not particularly limited.
As the antacid of present embodiment, metal oxide, metal hydroxides, metal carbonate or complex metal hydroxide can be used, suitably can select according to the amount of the acid produced and purposes.As above-mentioned antacid, specifically, the oxide compound, oxyhydroxide, carbonate, carboxylate salt, silicate, borate, phosphite, metaborate etc. of the periodic table of elements group II metals such as magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, hydrated barta, magnesiumcarbonate, barium carbonate, calcium carbonate, lime borate, Zinic stearas, calcium phthalate, Arizona bacilli, zinc oxide, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium borate, magnesium metaborate, calcium metaborate, barium metaborate can be enumerated; The oxide compound, subcarbonate, alkali formula carboxylate salt, alkali formula phosphite, alkali acid sulphite etc. of the periodic table of elements the 14th race's metals such as stannic oxide, basic carbonate tin, stearic acid tin, alkali formula phosphorous acid tin, alkali formula sulfurous acid tin, tri-lead tetroxide, silicon oxide, stearic acid silicon; Zinc oxide, aluminum oxide, aluminium hydroxide, ironic hydroxide (II); The complex metal hydroxides such as hydrotalcite compound; Aluminum hydroxide gel compound; Deng.They can be used alone one, also can more than two kinds used in combination.Wherein, be preferably magnesium hydroxide, magnesium oxide, zinc oxide, tri-lead tetroxide, calcium hydroxide, aluminium hydroxide, ironic hydroxide (II), calcium carbonate, hydrotalcite compound and/or its burned material, be more preferably hydrotalcite compound and/or its burned material.
In the present embodiment, hydrotalcite compound and burned material thereof, be have interlayer ion exchangeability and with the neutralization reaction of acid, the compound that forms lamellar morphologies.And, when for solar module, play and prevent from immersing water in solar cell sealing material, the acid that produced by solder flux enters into interlayer, in addition, the effect (catching effect hereinafter also referred to as acid, water) of solar cell sealing material, generating element deterioration is prevented by neutralizing.And acid, water catch effect and are determined by the size of electric density of the ion entering into interlayer, and the negatively charged ion that valence mumber is high, ionic radius is little is easy to enter into interlayer.
As having above-mentioned acid, water catches the compound of effect, except hydrotalcite compound, known metal oxides, metal hydroxides, metal carbonate etc., but these compounds often specific refractory power is high.Therefore, when adding in ethene-alpha-olefin copolymer, become greatly with the refringence of ethene-alpha-olefin copolymer, scattering of light, reflection and become opaque occur, efficiency of conversion reduces.The transparency of can seeking hydrotalcite compound in present embodiment improves and acid, water catch the efficient activity of effect, suppress further through time reduce with the adaptation of protection component and efficiency of conversion reduces.
In present embodiment, hydrotalcite compound preferably uses the hydrotalcite of general natural hydrotalcite, synthesis.
In present embodiment, the burned material of hydrotalcite compound can manufacture by being burnt till by hydrotalcite compound.This burned material plays high acid compared with hydrotalcite compound, water catches effect.In addition, burned material by catch acid, water, chemical constitution change, specific refractory power reduce, diminish with the refringence of ethene-alpha-olefin copolymer, therefore have the transparency through time improve tendency.
The hydrotalcite compound used in present embodiment is preferably the following hydrotalcite compound shown in general formula (A).
M 2+ 1-a·M 3+ a(OH) 2·An n- a/n·mH 2O (A)
(0.2≤a≤0.35,0≤m≤5, M 2+: be selected from Mg 2+, Zn 2+, Ni 2+, Ca 2+deng at least a kind of divalent metal ion, M 3+: be selected from Al 3+, Fe 3+deng at least a kind of 3 valence metal ion, An:n valency negatively charged ion)
In general formula (A), M 3+content ratio a is preferably 0.2 ~ 0.35.More than 0.2, easily manufacture hydrotalcite compound, below 0.35, can obtain with the refringence of ethene-alpha-olefin copolymer little, the solar cell sealing material that the transparency is better.In addition, as M 3+, be more preferably Al 3+.Moisture content m is preferably 0≤m≤5, is more preferably 0≤m≤1.In addition, negatively charged ion An n-kind be not particularly limited, but such as hydroxide ion, carbanion, silicate ion, organic carboxyl acid radical ion, organic sulfonic acid radical ion, organic phosphoric acid radical ion etc. can be enumerated.In addition, the index a in general formula (A) by by layered composite metal compound acid dissolve, can be analyzed by " luminescence of plasma spectroscopy apparatus SPS4000 (Seiko Electronics Industry Company system) " and obtains.
Hydrotalcite compound shown in general formula (A), average plate face diameter is preferably 0.02 ~ 0.9 μm.And, from the viewpoint of dispersed and transparent, be more preferably 0.02 ~ 0.65 μm.If be below above-mentioned higher limit, then transparency when being matched with ethene-alpha-olefin copolymer can be made to improve further.If be more than above-mentioned lower value, then the industrial productivity of hydrotalcite compound can be made to improve.
In addition, the plate face diameter of hydrotalcite compound is observed by scanning electron microscope, for obtaining the area equivalent circular diameter of hydrotalcite compound and the several averages obtained.
The specific refractory power of the hydrotalcite compound shown in general formula (A) is preferably 1.48 ~ 1.6.From the viewpoint of the transparency brought by the refringence with ethene-alpha-olefin copolymer, be more preferably 1.48 ~ 1.55.If be more than above-mentioned lower value, then the industrial productivity of hydrotalcite compound can be made to improve.On the other hand, if be below above-mentioned higher limit, then transparency when being matched with ethene-alpha-olefin copolymer, acid, water can be made to catch the persistence of effect and improve further.In addition, specific refractory power can measure based on JIS-K0062.Such as, using α-bromonaphthalene and DMF as solvent, can be measured by Baker process in 23 DEG C of uses " Abbérefractometer: 3T (Atago Inc.) ".
The average plate face diameter of burned material is preferably 0.02 ~ 0.9 μm.And, from the viewpoint of the dispersed and transparency, be more preferably 0.02 ~ 0.65 μm.If be below above-mentioned higher limit, then sour capturing ability when being matched with ethene-alpha-olefin copolymer is good.If be more than above-mentioned lower value, then can carry out the industrial production of hydrotalcite compound.
The specific refractory power of burned material is preferably 1.58 ~ 1.72.If be more than 1.58, then burn till and become abundant, crystal defect not easily occurs, and can suppress the deterioration of solar cell sealing material.In addition, if be less than 1.72, then transparency when being matched with ethene-alpha-olefin copolymer can be made to improve further.
The adsorptive capacity of the acetic acid of the hydrotalcite compound shown in general formula (A) and burned material thereof is preferably 0.1 ~ 0.8 μm of ol/g.If be 0.1 μm of more than ol, then can give full play to sour capturing ability.On the other hand, if be 0.8 μm of below ol, then can suppress the catalytic activity of filler, suppress the hydrolysis of resin.In addition, the adsorptive capacity of acetic acid can be obtained as follows: the ethylene glycol monomethyl ethereal solution 30ml adding the acetic acid of 0.02mol/L in above-mentioned layered composite metal compound 1g, carry out 1 hour half ultrasonic washing, it is made to be adsorbed in layered composite metal compound, by the potassium hydroxide solution of supernatant liquor 0.1 equivalent obtained by centrifugation, obtained by the back titration based on potentiometric titration.
Hydrotalcite compound and burned material thereof, BET specific surface area is preferably 1 ~ 200m 2/ g, is more preferably 1 ~ 160m 2/ g.If be more than above-mentioned lower value, then not easily occur with the Chemical bond of other additives such as UVA, the impact on other additive can be suppressed.If be below above-mentioned higher limit, then can suppress the alkalescence of hydrotalcite compound, can the deterioration of ethene suppressing-alpha-olefin copolymer.
The manufacturing process of hydrotalcite compound is described.
Can by by least a kind of aqueous metal salt in magnesium salt solution, zinc salt solution, nickel salt aqueous solution, calcium saline solution, mix with the alkaline aqueous solution containing negatively charged ion and aluminum saline solution, making pH is after the mixing solutions of the scope of 8 ~ 14, and the temperature range of this mixing solutions at 80 ~ 100 DEG C is carried out slaking to obtain.
PH in slaking reaction is preferably 10 ~ 14, is more preferably 11 ~ 14.If pH is more than above-mentioned lower value, then can obtains plate face diameter little, there is the hydrotalcite compound of appropriate thickness.
If curing temperature is the scope of 80 DEG C ~ 100 DEG C, then can obtain the hydrotalcite compound with appropriate plate face diameter.Preferred curing temperature is 85 ~ 100 DEG C.
The digestion time of the slaking reaction of hydrotalcite compound is not particularly limited, but is such as 2 ~ 24 hours.If be more than 2 hours, then can obtain plate face diameter little, there is the layered composite metal compound of appropriate thickness.If be less than 24 hours, then slaking is economical.
As the anion-containing alkaline aqueous solution of above-mentioned bag, preferably wrap the mixed base aqueous solution of the anion-containing aqueous solution and the alkali hydroxide aqueous solution.
As the anion-containing aqueous solution of bag, be preferably the aqueous solution of sodium carbonate, salt of wormwood, sodium phosphate, water glass, organic carboxylate, organic sulfonate, organophosphate etc.
As the alkali hydroxide aqueous solution, be preferably sodium hydroxide, potassium hydroxide, ammonia, aqueous solution of urea etc.
As the aqueous metal salt in present embodiment, sulfuric acid aqueous metal solution, chlorination aqueous metal solution or nitric acid aqueous metal solution etc. can be used, be preferably magnesium chloride brine.In addition, can substitute oxidized metal powder, hydroxide metal-powder slurry.
As the aluminum saline solution in present embodiment, aluminum sulfate aqueous solution, aluminum chloride aqueous solution and aluminum nitrate aqueous solution etc. can be used, be preferably aluminum sulfate aqueous solution, aluminum chloride aqueous solution.In addition, can substitute alumina powder, aluminium-hydroxide powder slurry.
Alkali aqueous solution containing negatively charged ion, order by merging with magnesium salt solution, zinc salt solution, nickel salt aqueous solution, at least a kind of aqueous metal salt in calcium saline solution and aluminum saline solution, be not particularly limited, each aqueous solution or slurry can be mixed simultaneously.Preferably add the aqueous solution or the slurry of at least a kind of aqueous metal salt and the aluminum saline solution be pre-mixed in magnesium salt solution, zinc salt solution, nickel salt aqueous solution, calcium saline solution in containing the alkali aqueous solution of negatively charged ion.
In addition, when adding each aqueous solution, can carry out in arbitrary situation of the situation of disposable this aqueous solution of interpolation or situation about dripping continuously.
The pH of the hydrotalcite compound shown in general formula (A) is preferably 8.0 ~ 10.0.If pH is more than 8.0, then with acid in and efficiency good.If pH is less than 10.0, then can suppress the deterioration of the ethene-alpha-olefin copolymer caused by the stripping of metal.In addition, the pH of hydrotalcite compound can measure by the following method.First, take in the erlenmeyer flask of 300ml by sample 5g, add the pure water 100ml boiled, heating, keeps about 5 minutes boil condition.Then, close the lid and let cool normal temperature, add the water being equivalent to decrement, again close the lid and vibrate 1 minute, leave standstill 5 minutes.Then, the pH of the supernatant liquor of gained can be measured according to JIS Z8802-7, the value of gained is set to the pH of hydrotalcite metallic compound.
In the manufacture of burned material, preferably hydrotalcite compound is burnt till at 200 ~ 800 DEG C, more preferably burn till at 250 ~ 700 DEG C.As long as firing time adjusts according to firing temperature, be not particularly limited, but be preferably 1 ~ 24 hour, be more preferably 1 ~ 10 hour.In addition, atmosphere when burning till can for oxidizing atmosphere, nonoxidizing atmosphere any one, but the gas with strong reducing action preferably not using hydrogen such.
(silane coupling agent)
The solar cell sealing material of present embodiment preferably comprises silane coupling agent further.The content of the silane coupling agent in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin copolymer 100 weight part, is preferably 0.1 ~ 5 weight part, is more preferably 0.1 ~ 4 weight part, is particularly preferably 0.1 ~ 3 weight part.
If the content of silane coupling agent is more than 0.1 weight part, then cementability improves.On the other hand, if the content of silane coupling agent is below 5 weight, then can suppress the addition for making silane coupling agent and ethene-alpha-olefin copolymer carry out the organo-peroxide of graft reaction when the lamination of solar module.Therefore, can suppress gelation when solar cell sealing material forcing machine being formed sheet and obtains, consequently, can suppress the torque of forcing machine, therefore the shaping of extrudate piece becomes easy.Owing to not producing jello in forcing machine, therefore do not have concavo-convex on the surface of sheet, the outward appearance of sheet is good.In addition, owing to not having gel, even if therefore apply voltage also do not produce the cracking caused by the jello of sheet inside, therefore puncture of insulation resistance is good.In addition, water vapour permeability is also good.
In addition, also there is condensation reaction in silane coupling agent itself sometimes, exists in solar cell sealing material as white stripes, and products appearance worsens, if but silane coupling agent is below 5 weight, then also can suppress the generation of white stripes.
Silane coupling agent can use known silane coupling agent, is not particularly limited.Specifically, vinyltriethoxysilane can be used, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group triethoxyl silane, to styryl Trimethoxy silane, APTES, 3-TSL 8330, N-2-(amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propyl group amine, N-phenyl-3-TSL 8330, 3-ureidopropyltriethoxysilane, 3-isocyanate group propyl-triethoxysilicane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl, 3-methacryloyloxypropyl methyl diethoxy silane, 3-acryloxypropyl Trimethoxy silane etc.Preferably can enumerate the good 3-glycidoxypropyltrime,hoxysilane of cementability, 3-glycidoxypropyl group triethoxyl silane, APTES, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl Trimethoxy silane, vinyltriethoxysilane.
(hindered amine system photostabilizer)
The solar cell sealing material of present embodiment preferably comprises hindered amine system photostabilizer further.By comprising hindered amine system photostabilizer, the free radical kind harmful to ethene-alpha-olefin copolymer can be caught, suppress the generation of new free radical.
As hindered amine system photostabilizer, two (2,2 can be used, 6,6-tetramethyl--4-piperidyl) sebate, poly-[{ 6-(1,1,3,3-tetramethyl butyl) amino-1,3,5-triazine-2,4-bis-base } { (2,2,6,6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidyl) imino-] etc. hindered amine system, hindered piperidine based compound etc.
In addition, the low molecular weight hindered amine system photostabilizer of following general formula (1) can also be used.
In above-mentioned general formula (1), R 1, R 2represent hydrogen, alkyl etc.R 1with R 2can be the same or different.R 1and R 2be preferably hydrogen or methyl.R 3represent hydrogen, alkyl, alkenyl etc.R 3be preferably hydrogen or methyl.
As the hindered amine system photostabilizer shown in above-mentioned general formula (1), specifically, 4-acryloxy-2 can be enumerated, 2, 6, 6-tetramethyl piperidine, 4-acryloxy-1, 2, 2, 6, 6-pentamethvl, 4-acryloxy-1-ethyl-2, 2, 6, 6-tetramethyl piperidine, 4-acryloxy-1-propyl group-2, 2, 6, 6-tetramethyl piperidine, 4-acryloxy-1-butyl-2, 2, 6, 6-tetramethyl piperidine, 4-methacryloxy-2, 2, 6, 6-tetramethyl piperidine, 4-methacryloxy-1, 2, 2, 6, 6-pentamethvl, 4-methacryloxy-1-ethyl-2, 2, 6, 6-tetramethyl piperidine, 4-methacryloxy-1-butyl-2, 2, 6, 6-tetramethyl piperidine, 4-crotons acyloxy-2, 2, 6, 6-tetramethyl piperidine, 4-crotonoyl Oxy-1-propyl group-2, 2, 6, 6-tetramethyl piperidine etc.
In addition, the high molecular hindered amine system photostabilizer shown in following formula can also be used.So-called high molecular hindered amine system photostabilizer, refers to that molecular weight is the hindered amine system photostabilizer of 1000 ~ 5000.
The content of the hindered amine system photostabilizer in the solar cell sealing material of present embodiment, relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part, be preferably 0.01 ~ 2.0 weight part, be more preferably 0.01 ~ 1.6 weight part, be particularly preferably 0.05 ~ 1.6 weight part.If the content of hindered amine system photostabilizer is more than 0.01 weight part, then weathering resistance and thermotolerance good.If the content of hindered amine system photostabilizer is below 2.0 weight parts, then can suppress the annihilation of the free radical produced by organo-peroxide, cementability, thermotolerance, crosslinking feature are good.
(hindered phenol system stablizer)
The solar cell sealing material of present embodiment preferably comprises hindered phenol system stablizer further.By comprising hindered phenol system stablizer, the free radical kind harmful to ethene-alpha-olefin copolymer can be caught in the presence of oxygen, suppress the generation of new free radical, can oxidative degradation be prevented.
As hindered phenol system stablizer, known compound can be used, can enumerate such as, 1, 1, 3-tri--(2-methyl-4-hydroxyl-5-tert-butyl-phenyl butane, 4, 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 2, 2-thiobis (4-methyl-6-tert-butylphenol), 7-octadecyl-3-(4 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl) propionic ester, four-[methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionate methane, tetramethylolmethane-four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1, 6-hexylene glycol-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2, two (just pungent sulfenyl)-6-(the 4-hydroxyl-3 of 4-, 5-di-tert-butyl amido)-1, 3, 5-triazine, three-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester, 2, 2-sulfo--di ethylene bis [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxyl)-hydrocinnamamide, 2, two [(pungent sulfenyl) the methyl]-ortho-cresol of 4-, 3, 5-di-tert-butyl-4-hydroxyl benzyl-phosphonic acid ester-diethyl ester, four [methylene radical (3, 5-di-t-butyl-4-hydroxy hydrocinnamate)] methane, octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 3, 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, 1-dimethyl ethyl]-2, 4-8, 10-tetra-oxaspiro [5.5] undecane etc.Wherein, tetramethylolmethane-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester is particularly preferably.
The content of the hindered phenol system stablizer in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin copolymer 100 weight part, be preferably 0.005 ~ 0.1 weight part, be more preferably 0.01 ~ 0.1 weight part, be particularly preferably 0.01 ~ 0.06 weight part.If the content of hindered phenol system stablizer is more than 0.005 weight part, then thermotolerance is good, in the heat-proof aging test under the high temperature of such as more than 120 DEG C, has the tendency of the xanthochromia that can suppress solar cell sealing material.If the content of hindered phenol system stablizer is below 0.1 weight part, then the crosslinking feature of solar cell sealing material is good, and thermotolerance, cementability are good.
In addition, under fixed temperature and humidity, if with have alkalescence hindered amine system photostabilizer and use, then the hydroxyl of hindered phenol stabilizer forms salt, form the two quinone methides of conjugation of quinone and dimerization, there is the tendency being easy to the xanthochromia causing solar cell sealing material, if but hindered phenol system stablizer is below 0.1 weight part, then can suppress the xanthochromia of solar cell sealing material.
(phosphorus system stablizer)
The solar cell sealing material of present embodiment preferably comprises phosphorus system stablizer further.If comprise phosphorus system stablizer, then the decomposition of organo-peroxide when can suppress extrusion moulding, can obtain the sheet that outward appearance is good.If comprise hindered amine system photostabilizer, hindered phenol system stablizer, then also can fall into oblivion the free radical of generation, the sheet that production outward appearance is good, but sheet is extruded in operation and is consumed stablizer, has the tendency that the long-term reliability such as thermotolerance, weathering resistance reduces.
As phosphorus system stablizer, known compound can be used, can enumerate such as, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, two [2,4-two (1,1-dimethyl ethyl)-6-aminomethyl phenyl] ethyl ester phosphorous acid, four (2,4-di-tert-butyl-phenyl) [1,1-xenyl]-4,4 '-two base biphosphinate and two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites etc.Wherein, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is preferably.
The content of the phosphorus system stablizer in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin copolymer 100 weight part, is preferably 0.005 ~ 0.5 weight part, is more preferably 0.01 ~ 0.5 weight part, is particularly preferably 0.02 ~ 0.2 weight part.If the content of phosphorus system stablizer is more than 0.005 weight part, then the decomposition of organo-peroxide when can suppress extrusion moulding, can obtain the sheet that outward appearance is good.In addition, thermotolerance is good, in the heat-proof aging test under the high temperature of such as more than 120 DEG C, has the tendency of the xanthochromia that can suppress solar cell sealing material.If the content of phosphorus system stablizer is below 0.5 weight part, then the crosslinking feature of solar cell sealing material is good, and thermotolerance, cementability are good.In addition, have no the impact of the acid band produced by the decomposition of phosphorus system stablizer, also metallic corrosion does not occur.
In addition, although there is the stablizer in same a part with phosphorous acid ester structure and hindered phenol structure, but in large quantities containing in the composition of organo-peroxide as the solar cell sealing material of present embodiment, suppress the performance of decomposition of organo-peroxide insufficient during extrusion moulding, have and generate gel and the tendency that can not get the good sheet of outward appearance.
(UV light absorber)
The solar cell sealing material of present embodiment preferably comprises UV light absorber further.
The content of the UV light absorber in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin copolymer 100 weight part, is preferably 0.005 ~ 5 weight part.If the content of UV light absorber is in above-mentioned scope, then the balancing good of weathering stability, crosslinking feature, therefore preferably.
As UV light absorber, specifically, the benzophenone series such as 2-hydroxyl-4-n-octyl oxygen base benzophenone, ESCALOL 567,2,2-dihydroxyl-4-methoxy benzophenones, 2-hydroxyl-4-methoxyl group-4-carboxyl benzophenone, Octabenzone can be used; The benzotriazole systems such as 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole; The salicylate such as salol, p-octylphenyl salicylate system UV light absorber.
(other additive)
Form in the resin combination of the solar cell sealing material of present embodiment, in the scope not damaging object of the present invention, can suitably containing the various compositions beyond the above each composition described in detail.Can enumerate such as, the various polyolefine beyond ethene-alpha-olefin copolymer, polystyrene, ethene based block copolymer, acrylic polymer etc.The content of the various compositions in solar cell sealing material, relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part, is preferably 0.0001 ~ 50 weight part, is more preferably 0.001 ~ 40 weight part.In addition, also can suitably containing more than one the additive in the various resin be selected from addition to the polyolefin and/or various rubber, softening agent, weighting agent, pigment, dyestuff, static inhibitor, antiseptic-germicide, mould inhibitor, fire retardant, crosslinking coagent, other heat-resisting stabilizing agent and dispersion agent etc. except hindered phenol system stablizer and phosphorus system stablizer.
As other heat-resisting stabilizing agent except hindered phenol system stablizer and phosphorus system stablizer, specifically, 3-hydroxyl-5 can be enumerated, the lactone system heat-resisting stabilizing agents such as the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol, myristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate, two-tridecyl thiodipropionate, tetramethylolmethane-four-(β-lauryl-thiopropionate), 2-mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, 2 mercaptomethyl benzimidazole, the zinc salt of 2 mercaptomethyl benzimidazole, 4, 4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 2, 6-di-t-butyl-4-(4, two (the pungent sulfenyl)-1 of 6-, 3, 5-triazine-2-base is amino) the sulphur system heat-resisting stabilizing agent such as phenol, amine system heat-resisting stabilizing agent etc.
Particularly, when containing crosslinking coagent, the content of the crosslinking coagent in the solar cell sealing material of present embodiment, relative to ethene-alpha-olefin copolymer 100 weight part, is preferably 0.05 ~ 5 weight part, is more preferably 0.1 ~ 3 weight part.If the content of crosslinking coagent is in above-mentioned scope, then can has the crosslinking structure of appropriateness, thermotolerance, mechanical properties, cementability can be improved, therefore preferably.
As crosslinking coagent, the known crosslinking coagent generally used relative to ethylene series resin can be used.Such crosslinking coagent is the compound in molecule with more than two double bonds.Specifically, the mono acrylic esters such as tert-butyl acrylate, lauryl acrylate, vinylformic acid hexadecyl ester, stearyl acrylate base ester, 2-methoxyethyl acrylate, ethyl carbitol acrylate, methoxyl group tripropylene glycol acrylate can be enumerated; The monomethacrylates such as Tert-butyl Methacrylate, lauryl methacrylate, cetyl ester, stearyl methacrylate, methoxyl group glycolmethacrylate, methoxy polyethylene glycol methacrylate-styrene polymer; 1,4-butylene glycol diacrylate, 1, the diacrylates such as 6-hexanediyl ester, 1,9-nonanediol diacrylate, neopentylglycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethyleneglycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate; 1,3-butylene glycol dimethacrylate, 1, the dimethacrylates such as 6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, neopentylglycol dimethacrylate, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, polyethylene glycol dimethacrylate; The triacrylates such as Viscoat 295, tetramethylol methane triacrylate, pentaerythritol triacrylate; The trimethacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate methacrylic ester; The tetraacrylate such as tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate; The di vinyl aromatic such as Vinylstyrene, two-isopropenylbenzene compounds of group; The cyanurate such as triallylcyanurate, cyanacrylate; The diallyl compounds such as diallyl phthalate; Triallyl compound; Paraquinonedioxime, p, p ' oxime such as-dibenzoyl quininie dioxime; The maleimides such as phenyl maleimide.
In these crosslinking coagents, the more preferably triacrylate such as diacrylate, dimethacrylate, di vinyl aromatic compounds of group, Viscoat 295, tetramethylol methane triacrylate, pentaerythritol triacrylate; The trimethacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate methacrylic ester; The tetraacrylate such as tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate; The cyanurate such as triallylcyanurate, cyanacrylate; The diallyl compounds such as diallyl phthalate; Triallyl compound; Paraquinonedioxime, p, p ' oxime such as-dibenzoyl quininie dioxime; The maleimides such as phenyl maleimide.In addition particularly preferably be cyanacrylate in these crosslinking coagents, the bubble of the solar cell sealing material after lamination occurs, the balance of crosslinking feature is the most excellent.
The solar cell sealing material of present embodiment, preferably by relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part, the content of organo-peroxide is 0.1 ~ 3 weight part, the content of hindered phenol system stablizer is 0.005 ~ 0.1 weight part, the content of hindered amine system photostabilizer is 0.01 ~ 2.0 weight part, and the content of phosphorus system stablizer is the resin combination formation of 0.005 ~ 0.5 weight part.
In addition, the solar cell sealing material of present embodiment, particularly preferred mode is by relative to above-mentioned ethene-alpha-olefin copolymer 100 weight part, the content of organo-peroxide is 0.2 ~ 2.5 weight part, the content of hindered phenol system stablizer is 0.01 ~ 0.06 weight part, the content of hindered amine system photostabilizer is 0.05 ~ 1.6 weight part, and the content of phosphorus system stablizer is the resin combination formation of 0.02 ~ 0.2 weight part.
The solar cell sealing material of present embodiment; excellent to the long-term reliability under the cementability of metal line and solder and fixed temperature and humidity while keeping the transparency, and protect the balancing good of the cementability of the various solar cell components such as component, membrane electrode, aluminium, solar cell device, thermotolerance, the balance of extrusion moulding and crosslinking feature, flexibility, outward appearance, weathering resistance, volume intrinsic resistance, electrical insulating property, water vapour permeability, electrode corrosion, technology stability with face side transparent protection member, rear side.Therefore, be suitable as the solar cell sealing material of known solar module and use.Normally used method can be utilized as the manufacture method of the solar cell sealing material of present embodiment, but carry out melt blending to manufacture preferably by kneader, Banbury mixer, forcing machine etc.Particularly preferably by manufacturing by quantity-produced forcing machine.
Solar cell sealing material, to be sheet be also its global shape one of preferred embodiment.In addition, there is sheet that at least one deck formed by above-mentioned solar cell sealing material and the solar cell sealing material obtained with other layer of Composite also can be applicable to using.The thickness of the layer of solar cell sealing material is generally 0.01 ~ 2mm, is preferably 0.05 ~ 1.5mm, is more preferably 0.1 ~ 1.2mm, more preferably 0.2 ~ 1mm, is particularly preferably 0.3 ~ 0.9mm, most preferably be 0.3 ~ 0.8mm.If thickness is within the scope of this, then can suppress the breakage of the face side transparent protection member, solar cell device, membrane electrode etc. in lamination, and, guarantee sufficient light transmittance, thus high light generated energy can be obtained.In addition, the laminated into type of the solar module under low temperature can be carried out, therefore preferably.
The forming method of solar cell sealing material sheet is not particularly limited, but can adopt known various forming method (cast molding, extrudate piece is shaping, inflation is shaping, injection molding, compressed moulding, calendering formation etc.).
Wherein, following methods is most preferred embodiment.First, by ethene-alpha-olefin copolymer, organo-peroxide, antacid (antacid that can be also masterbatch) and more than a kind additive being selected from as required in silane coupling agent, hindered amine system photostabilizer, hindered phenol system stablizer, phosphorus system stablizer, UV light absorber, crosslinking coagent and other additive, such as, in the bags such as plastics bag, carry out the blending of manpower, use the stirring mixers such as Henschel mixer, rotating cylinder, high-speed mixer to carry out blending.Then, put into by the resin combination of gained in the hopper of extrudate piece forming machine, it is shaping to carry out extrudate piece while carrying out melting mixing, obtains the solar cell sealing material of sheet.
In addition, utilize forcing machine once to granulate with the resin combination fitted in, and then when carrying out sheet by extrusion moulding, compression moulding, generally speaking pass through from water layer, or use the forcing machine cooling line material of imderwater cutting machine formula, cut and obtain particle.Therefore, due to attachment of moisture, therefore the deterioration of additive particularly silane coupling agent occurs, and such as, when again carrying out sheet with forcing machine, silane coupling agent condensation reaction is each other carried out, and has the tendency that cementability reduces, therefore not preferred.
In addition, by ethene-alpha-olefin copolymer and except organo-peroxide, additive (hindered phenol system stablizer beyond silane coupling agent, phosphorus system stablizer, hindered amine system photostabilizer, the stablizers such as UV light absorber) use forcing machine masterbatch in advance after, blending organo-peroxide, silane coupling agent, and again with forcing machine etc. carry out sheet shaping time, also due to hindered phenol system stablizer, phosphorus system stablizer, hindered amine system photostabilizer, the stablizers such as UV light absorber two degree pass through forcing machine, therefore stablizer deterioration is had, weathering resistance, the tendency that the long-term reliabilities such as thermotolerance reduce, therefore not preferred.
As extrusion temperature scope, extrusion temperature is 100 ~ 130 DEG C.By making extrusion temperature be more than 100 DEG C, then the productivity of solar cell sealing material can be made to improve.If make extrusion temperature be less than 130 DEG C, then become when resin combination being obtained solar cell sealing material with extruding Bigpian and not easily gelation occurs.Therefore, the rising of the torque of forcing machine can be prevented, make sheet easily shaping.In addition, not easily produce concavo-convex owing to becoming on the surface of sheet, therefore can prevent deteriorated appearance.In addition, can suppress to produce cracking in applying voltage time slice inside, therefore can prevent the reduction of breakdown voltage.In addition, the reduction of water vapour permeability can also be suppressed.In addition, not easily produce concavo-convex owing to becoming on sheet surface, therefore when the lamination process of solar module, protect the adaptation of component to become good with face side transparent protection member, unit, electrode, rear side, cementability can be made to improve.
In addition, be when being such as less than 10g/10 minute at the MFR of ethene-alpha-olefin copolymer, use by by molten resin with (stack) rolling of warmed-up metallic roll thus make desired by the sheet of thickness, the calendering formation machine of film, carry out ethene-alpha-olefin copolymer, with silane coupling agent, organo-peroxide, UV light absorber, photostabilizer, heat-resisting stabilizing agent and the melting mixing of other additive that uses as required while carry out calendering formation, also can obtain the solar cell sealing material of sheet.
As calendering formation machine, known various calendering formation machine can be used, mixing roll, tri-roll press machine, four-roll calender can be used.As four-roll calender, I type, S type, inverted L shape, Z-type, tiltedly Z-type etc. can be used especially.In addition, also preferred before imposing on stack, in advance vinylite composition is heated to the temperature of appropriateness, such as, arranging Banbury mixer, kneader, forcing machine etc. is also one of preferred embodiment.The temperature range of calendering formation preferably makes roll temperature be generally 40 ~ 100 DEG C.
In addition, embossing processing can be implemented to the surface of the sheet of solar cell sealing material (or layer).Processed the sheet surface decorating solar cell sealing material by embossing, thus can prevent sealing material sheet each other or the adhesion of sealing material sheet and other sheet etc.In addition, embossing reduces owing to making the storage elastic modulus of solar cell sealing material (solar cell sealing material sheet), therefore in the buffering that will become when solar cell sealing material sheet and solar cell device lamination solar cell device etc., thus the breakage of solar cell device can be prevented.
The total volume V of the recess of the per unit area of the sheet of solar cell sealing material hwith the apparent volume V of the sheet of solar cell sealing material aper-cent V h/ V avoidage P (%) shown in × 100 is preferably 10 ~ 50%, is more preferably 10 ~ 40%, and more preferably 15 ~ 40%.In addition, the apparent volume V of the sheet of solar cell sealing material aobtain by unit surface is multiplied by the maximum ga(u)ge of solar cell sealing material.If voidage P is more than 10%, then the Young's modulus of solar cell sealing material can be made fully to reduce, 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 system solar cell, the cracking of solder can prevent silicon unit, being fixed silicon unit and electrode, for film system solar cell, the cracking of silver electrode can be prevented.That is, if the voidage of solar cell sealing material is more than 10%, even if then when being applied with pressure partly to solar cell sealing material, the protuberance being applied with pressure also can be out of shape in the mode shriveled.Therefore, when lamination process, even if be such as applied with large pressure partly relative to silicon unit etc., also can prevent silicon unit from ftractureing.In addition, if the voidage of solar cell sealing material is more than 10%, then the passage of air can be guaranteed, therefore can be degassed well when lamination process.Therefore, residual air in solar module and deteriorated appearance can be prevented, or the corrosion of generating electrodes due to the moisture in residual air when life-time service.In addition, when lamination, the space that the resin combination of flowing produces tails off, and therefore can prevent the outside of each adherend being exuded to solar module and pollution layer press.
On the other hand, if voidage P is less than 80%, then air can be degassed well when the pressurization of lamination process, therefore can prevent residual air in solar module.Therefore, the deterioration of the outward appearance of solar module can be prevented, also can not the corrosion of generating electrodes due to the moisture in residual air when life-time service.In addition, air can be degassed well when the pressurization of lamination process, and therefore the bond area of solar cell sealing material and adherend increases, and can obtain sufficient bonding strength.
Voidage P can obtain by calculating as following.Implement the apparent volume V of the solar cell sealing material of embossing processing a(mm 3) by the maximum ga(u)ge t of solar cell sealing material max(mm) with unit surface (such as 1m 2=1000mm × 1000mm=10 6mm 2) long-pending, calculate as following formula (12).
V A(mm 3)＝t max(mm)×10 6(mm 2) (12)
On the other hand, the actual volume V of the solar cell sealing material of this unit surface 0(mm 3) pass through the proportion ρ (g/mm of the resin of formation solar cell sealing material 3) and per unit area (1m 2) the actual weight W (g) of solar cell sealing material substitute into following formula (13) and calculate.
V 0(mm 3)＝W/ρ (13)
The total volume V of the recess of the per unit area of solar cell sealing material h(mm 3), as shown in following formula (14), by from " the apparent volume V of solar cell sealing material a" in deduct " actual volume V 0" calculate.
V H(mm 3)＝V A-V 0＝V A-(W/ρ) (14)
Therefore, voidage (%) can be obtained as follows.
Voidage P (%)=(V h/ V a) × 100
＝((V A-(W/ρ))/V A)×100
＝(1-W/(ρ·V A))×100
＝(1-W/(ρ·t max·10 6))×100
Voidage P (%) can be obtained by above-mentioned calculating formula, but also can by carrying out microscope photographing to the cross section of the solar cell sealing material of reality, the face that implements embossing processing, and carries out image procossing etc. and obtain.
To be processed by embossing and the degree of depth of the recess formed is preferably 20 ~ 95% of the maximum ga(u)ge of solar cell sealing material, be more preferably 50 ~ 95%, be more preferably 65 ~ 95%.Sometimes by the maximum ga(u)ge t of the degree of depth D of recess relative to sheet maxper-cent be called " degree of depth rate " of recess.
The degree of depth of the recess of so-called embossing processing, represent by embossing process the male and fomale(M&F) of the solar cell sealing material obtained, the difference of height D in the most deep of the top of protuberance and recess.In addition, the maximum ga(u)ge t of so-called solar cell sealing material maxwhen carrying out embossing processing to a face of solar cell sealing material, represent (the solar cell sealing material thickness direction) distance from the top of the protuberance in a face to another face, when implementing embossing processing to two faces of solar cell sealing material, represent (solar cell sealing material thickness direction) distance of the top of the protuberance from the top of the protuberance in a face to another face.
Embossing processing can be implemented the one side of solar cell sealing material, also can implement two sides.When increasing the degree of depth of recess of embossing processing, preferably only formed in the one side of solar cell sealing material.When only implementing embossing processing to the one side of solar cell sealing material, the maximum ga(u)ge t of solar cell sealing material maxfor 0.01mm ~ 2mm, be preferably 0.05 ~ 1mm, be more preferably 0.1 ~ 1mm, more preferably 0.15 ~ 1mm, more preferably 0.2 ~ 1mm, more preferably 0.2 ~ 0.9mm, be particularly preferably 0.3 ~ 0.9mm, most preferably be 0.3 ~ 0.8mm.If the maximum ga(u)ge t of solar cell sealing material maxwithin the scope of this, then can suppress the breakage of the face side transparent protection member, solar cell device, membrane electrode etc. in lamination, even if the laminated into type of solar module also can be carried out in lower temperature, therefore preferably.In addition, solar cell sealing material can guarantee sufficient light transmittance, and the solar module employing this solar cell sealing material has high light generated energy.
In addition, this sheet can be used as solar cell sealing material with the leaflet form cut into according to solar module size or the roll form that can cut according to size before being about to make solar module.As the solar cell sealing material (solar cell sealing material sheet) of the sheet of the preferred embodiment of the present invention as long as have the layer that at least one deck formed by solar cell sealing material.Therefore, the number of plies of the layer formed by the solar cell sealing material of present embodiment can be one deck, also can be more than two layers.The viewpoint reduced costs from making structure simple, and the boundary reflection of doing one's utmost between reducing layer and effectively utilize the considerations such as the viewpoint of light, be preferably one deck.
Solar cell sealing material sheet, the layer that can only be formed by the solar cell sealing material of present embodiment is formed, and also can have the layer (following, to be also designated as " other layer ") beyond the layer containing solar cell sealing material.As the example of other layer, if according to object classification, then the hard coat, adhesive linkage, anti-reflection layer, gas barrier layer, stain-proofing layer etc. for front or back-protective can be enumerated.If according to material classification, then can enumerate the layer formed by uv curing resin, the layer formed by thermosetting resin, the layer formed by polyolefin resin, the layer formed by carboxyl acid modified polyolefin resin, the layer formed by fluorine resin, the layer by cyclic olefin (being total to) polymer formation, the layer etc. that formed by mineral compound.
The layer formed by the solar cell sealing material of present embodiment and the position relationship of other layer are not particularly limited, and suitably select preferred layer to form according to the relation with object of the present invention.That is, other layer can be arranged between more than the 2 layers layers formed by solar cell sealing material, also can be arranged on the outermost layer of solar cell sealing material sheet, also can be arranged on place in addition.In addition, only other layer can be set in the one side of the layer formed by solar cell sealing material, also other layer can be set on two sides.The number of plies of other layer is not particularly limited, and can arrange other layer of the arbitrary number of plies, also can not arrange other layer.
The viewpoint reduced costs from making structure simple, boundary reflection and effectively utilize the considerations such as the viewpoint of light is reduced with doing one's utmost, only otherwise arrange other layer, and only with the layer making solar cell sealing material sheet that the solar cell sealing material by present embodiment is formed.But, if be necessary according to the relation with object or other useful layer, as long as then suitably arrange other such layer.
For the laminating method of the layer formed by the solar cell sealing material of present embodiment when arranging other layer and other layer, be not particularly limited, but be preferably known melt extruder coextrusion such as using cast molding machine, extrudate piece forming machine, inflation forming machine, injection moulding machine and obtain the method for multilayer body, or on one deck shaping in advance melting or another layer of heated lamination and obtain the method for multilayer body.
In addition, can by employing suitable caking agent (such as, maleic anhydride modified polyolefin resin (the trade(brand)name " ADOMER (registered trademark) " of Mitsui Chemicals, Inc., the trade(brand)name " MODIC (registered trademark) " etc. of Mitsubishi Chemical Ind), unsaturated polyolefin etc. low (non-) crystallinity soft polymer, with the acrylic acid series caking agent that ethene/acrylic ester/maleic anhydride terpolymer (trade(brand)name " Bondine (registered trademark) " etc. of Zhu Hua cdF chemical company) is representative, Ethylene/vinyl acetate based copolymer, or comprise their adhesive resin composition etc.) dry lamination method or lamination methods etc. carry out lamination.As caking agent, preferably use the caking agent with the thermotolerance of about 120 ~ 150 DEG C, Polyester or urethane adhesive etc. can be illustrated as the caking agent be applicable to.In addition, in order to improve two-layer cementability, such as, silane system coupling processing, titanium system coupling processing, corona treatment, Cement Composite Treated by Plasma etc. can be used.
2. about solar module
Solar module, can enumerate such as, usually, is clamped and lamination the solar cell device solar cell sealing material sheet formed by polycrystal silicon etc., and then by crystal type solar module that two sides in table covers with screening glass.That is, typical solar module is the such formation of solar module screening glass (face side transparent protection member)/solar cell sealing material/solar cell device/solar cell sealing material/solar module screening glass (rear side protection component).
But, as solar module one of preferred embodiment of the present invention, be not limited to above-mentioned formation, in the scope not damaging object of the present invention, suitably can omit a part for above-mentioned each layer, or layer other than the above is suitably set.As layer other than the above, such as adhesive linkage, impact absorbing layer, coating layer, anti-reflection layer, back side reflecting layer and light diffusion layer etc. again can be enumerated.These layers are not particularly limited, but can consider to arrange the object of each layer, characteristic and arranging in position.
(solar module of crystalline silicon)
Fig. 1 is the sectional view of the embodiment schematically showing solar module of the present invention.In addition, in FIG, an example of the formation of the solar module 20 of crystalline silicon is shown.As shown in Figure 1; solar module 20 has the solar cell device 22 of the multiple crystalline silicon be electrically connected by interconnector 29, a pair face side transparent protection member 24 clamping this solar cell device 22 and rear side protection component 26, between these protection component and multiple solar cell devices 22, be filled with sealing ply 28.Sealing ply 28 is by after the sealing material laminating used for solar batteries making present embodiment, adds thermo-compressed and obtains, connecting with the electrode of the sensitive surface and the back side that are formed at solar cell device 22.So-called electrode, is the collector component formed respectively at sensitive surface and the back side of solar cell device 22, comprises current collection line described later, attached lug bus and back electrode layer etc.
Fig. 2 is the orthographic plan schematically showing the sensitive surface of solar cell device and a configuration example at the back side.In fig. 2, an example of the sensitive surface 22A of solar cell device 22 and the formation of back side 22B is shown.As shown in Fig. 2 (A), at the sensitive surface 22A of solar cell device 22, be formed with the many current collection lines 32 being formed as wire and collect electric charge with from current collection line 32 and attached lug bus (bus-bar) 34A be connected with interconnector 29 (Fig. 1).In addition, as shown in Fig. 2 (B), at the back side 22B of solar cell device 22, whole face is formed with conductive layer (backplate) 36, is formed thereon and collects electric charge and attached lug bus (bus-bar) 34B be connected with interconnector 29 (Fig. 1) from conductive layer 36.The live width of current collection line 32 is such as about 0.1mm, and the live width of attached lug bus 34A is such as about 2 ~ 3mm, and the live width of attached lug bus 34B is such as about 5 ~ 7mm.The thickness of current collection line 32, attached lug bus 34A and attached lug bus 34B is such as about 20 ~ 50 μm.
Current collection line 32, attached lug bus 34A and attached lug bus 34B preferably comprise the high metal of electroconductibility.Comprise gold and silver, copper etc. in the example of the metal that such electroconductibility is high, but from considerations such as electroconductibility, aspects that erosion resistance is high, be preferably silver, silver compound, containing silver-colored alloy etc.Conductive layer 36 not only comprises the high metal of electroconductibility, makes the photoelectric transformation efficiency of solar cell device improve the considerations such as such viewpoint, also preferably comprise the high composition of light reflective, such as aluminium from the luminous reflectance made suffered by sensitive surface.Current collection line 32, attached lug bus 34A, attached lug bus 34B and conductive layer 36 are by after the conduction material coatings comprising the high metal of above-mentioned electroconductibility is become the coating thickness of 50 μm by such as screen painting by the sensitive surface 22A of solar cell device 22 or back side 22B, drying, is formed at such as 600 ~ 700 DEG C of sintering as required.
Face side transparent protection member 24, owing to being configured in sensitive surface side, therefore needs for transparent.In the example of face side transparent protection member 24, comprise transparency glass plate, transparent resin film etc.On the other hand, rear side protection component 26 does not need for transparent, and its material is not particularly limited.In the example of rear side protection component 26, comprise glass substrate, plastic film etc., but from the viewpoint of weather resistance, the transparency, be applicable to using glass substrate.
Solar module 20 can be obtained by arbitrary manufacture method.Solar module 20, such as, can be obtained by following operation: obtain by the operation of rear side protection component 26, solar cell sealing material, multiple solar cell device 22, solar cell sealing material and face side the transparent protection member 24 successively multilayer body of lamination; This multilayer body is carried out pressurization by laminating machine etc. makes it fit, the operation simultaneously heated as required; After above-mentioned operation, and then as required to multilayer body heat treated, by the operation that above-mentioned sealing material is solidified.
In solar cell device 22, be usually configured with the collecting electrodes of the electricity for taking out generation.In the example of collecting electrodes, comprise bus bar electrode, finger electrode etc.Generally speaking, collecting electrodes can adopt the structure on the two sides of the front and back being configured in solar cell device, if but at sensitive surface configuration collecting electrodes, then collecting electrodes covers light, therefore may produce the such problem of decrease of power generation.
In addition, in order to make generating efficiency improve, the back contacted solar cell element do not needed at sensitive surface configuration collecting electrodes can be used.In a form of back contacted solar cell element, in the rear side set by the opposition side of the sensitive surface of solar cell device, be arranged alternately p doped region and n doped region.In other form of back contacted solar cell element, in the substrate being provided with communicating pores (through hole), form p/n engage, form the doped layer of (sensitive surface) side, surface until the bore periphery portion of through-hole wall and rear side, the electric current of sensitive surface is taken out in side overleaf.
Generally speaking, in solar cell system, above-mentioned solar module is connected in series several to tens of, even the small-scale system of house is also used with 50V ~ 500V, uses with 600 ~ 1000V in the large-scale system being called as large-sized solar generating.For the housing of solar module, use aluminium chassis etc. for the purpose of intensity maintenance etc., the situation that from the viewpoint of in safety, aluminium chassis is grounded (earth) is many.Consequently, by solar cell power generation, between the face side transparent protection member face low with sealing material phase ratio resistance and solar cell device, produce by the voltage difference caused that generates electricity.
Consequently, for the solar cell sealing material be sealed between generator unit and face side transparent protection member or aluminium chassis, the electrical specification that high electrical insulating property, high resistance etc. are good is required.
(solar module of thin film silicon system (amorphous silicon system))
The solar module of thin film silicon system can be, (1) is by the module of face side transparent protection member (glass substrate)/Thinfilm solar cell component/sealing ply/rear side protection component successively lamination; (2) by the module etc. of face side transparent protection member/sealing ply/Thinfilm solar cell component/sealing ply/rear side protection component successively lamination.Face side transparent protection member, rear side protection component and sealing ply same with the situation of above-mentioned " solar module of crystalline silicon ".
(1) Thinfilm solar cell component in form such as comprises transparent electrode layer/pin type silicon layer/back electrode layer successively.In the example of transparent electrode layer, comprise In 2o 3, SnO 2, ZnO, Cd 2snO 4, ITO is (at In 2o 3in with the addition of Sn and obtain) etc. semi-conductor system oxide compound.Back electrode layer comprises such as Ag films layer.Each layer is by plasma CVD (chemical vapour deposition) method, sputtering method and being formed.Sealing ply configures in the mode connected with back electrode layer (such as Ag films layer).Transparent electrode layer is owing to being formed on face side transparent protection member, and therefore sealing ply often can not be configured between face side transparent protection member and transparent electrode layer.
(2) metal film layer (such as, Ag films layer) that the Thinfilm solar cell component of form comprises such as transparent electrode layer/pin type silicon layer/tinsel successively or is configured on thermotolerance polymeric membrane.In the example of tinsel, comprise stainless steel steel foil etc.In the example of thermotolerance polymeric membrane, comprise polyimide film etc.Transparent electrode layer and pin type silicon layer are formed by CVD, sputtering method as described above.That is, the pin type silicon layer metal film layer that is formed at tinsel or configures on thermotolerance polymeric membrane; And then transparent electrode layer is formed at pin type silicon layer.In addition, the metal film layer be configured on thermotolerance polymeric membrane also can be formed by CVD, sputtering method.
In this case, sealing ply is configured between transparent electrode layer and face side transparent protection member respectively; With tinsel or thermotolerance polymeric membrane and rear side are protected between component.Like this, the sealing ply obtained by solar cell sealing material connects with the electrode of the current collection line of solar cell device, attached lug bus and conductive layer etc.In addition the Thinfilm solar cell component of the form of (2), because silicon layer is thinner than the solar cell device of crystalline silicon, therefore not easily damaged due to the impact from outside when pressurization when solar module manufactures, above-mentioned module work.Therefore, compared with used with the solar module of crystalline silicon, the flexibility of the solar cell sealing material that film solar battery module is used can be low.On the other hand, the electrode due to above-mentioned Thinfilm solar cell component is metal film layer as described above, and therefore when due to corrosion when deterioration, generating efficiency may significantly reduce.
In addition, as other solar module, the solar module employing silicon in solar cell device is had.Employ in solar cell device in the solar module of silicon, mixed type (HIT type) solar module by silicon metal and amorphous silicon lamination can be enumerated, by many mating types (tandem type) solar module of silicon layer laminations different for absorbing wavelength region, rear side set by the opposition side of the sensitive surface of solar cell device is alternately provided with the back contacted solar cell module of p doped region and n doped region, by the spherical silicon type solar module etc. that countless spherical silicon particle (diameter about 1mm) combines with the concave mirror (doubling as electrode) of the diameter 2 ~ 3mm improving light gathering.In addition, employing in solar cell device in the solar module of silicon, also can enumerating the field effect type solar module etc. with the structure effect with the p-type window layer of the amorphous silicon type of pin connected structure being in the past replaced as " inversion layer brought out by field-effect " by " transparency electrode by having insulated ".In addition, the GaAs system solar module that solar cell device employs the GaAs of monocrystalline can be enumerated; As solar cell device, replace silicon and employ the CIS being called as the I-III-VI group compound of chalcopyrite system or CIGS (chalcopyrite system) solar module that are made up of Cu, In, Ga, Al, Se, S etc.; CdTe-CdS system solar cell, the Cu of Cd compound film is employed as solar cell device 2znSnS 4(CZTS) solar module etc.The solar cell sealing material of present embodiment can be used as the solar cell sealing material of these all solar modules.
Particularly, be stacked in the sealing sheet material layers under the photovoltaic cell forming solar module, need that there is the cementability with the sealing sheet material layers on the top being stacked in photovoltaic cell, electrode, back-protective layer.In addition, in order to keep the smoothness at the back side of the solar cell device as photovoltaic cell, need that there is thermoplasticity.In addition, in order to protect the solar cell device as photovoltaic cell, the excellence such as scuff resistance, impact absorbency is needed.
As above-mentioned sealing sheet material layers, preferably there is thermotolerance.When manufacturing particularly preferably in solar module, can not owing to vacuumizing and adding the life-time service of the heat effect, solar module etc. in laminating of thermo-compressed etc. time the heat effect etc. of sunlight etc., and the resin combination making formation seal sheet material layers goes bad, or deteriorated or decomposition.Suppose the strippings such as the additive that this resin combination comprises or generate resolvent, then they act on the electromotive force face (component side) of solar cell device, make its deterioration such as function, performance.Therefore, the characteristic that thermotolerance has as the sealing sheet material layers of solar module is absolutely necessary.
In addition, the preferred moisture resistance of above-mentioned sealing sheet material layers is excellent.In this case, can prevent the moisture of the rear side from solar module through, can prevent the photovoltaic cell of solar module burn into deterioration.
Above-mentioned sealing sheet material layers is different from the filling oxidant layer be stacked on photovoltaic cell, not necessarily needs to have the transparency.The solar cell sealing material of present embodiment has above-mentioned characteristic, can be suitable as the solar cell sealing material of thin film solar cell module of the solar cell sealing material of the rear side of crystal type solar module, not resistance to moisture penetration.
The solar module of present embodiment, in the scope not damaging object of the present invention, can suitably have arbitrary component.Typically, adhesive linkage, impact absorbing layer, coating layer, anti-reflection layer, back side reflecting layer, light diffusion layer etc. again can be set, but be not limited to these.The position arranging these layers is not particularly limited, and can consider to arrange the object of such layer and the characteristic of such layer, arranges in position.
(solar module face side transparent protection member)
The solar module face side transparent protection member that solar module is used; be not particularly limited; but owing to being positioned at the outermost layer of solar module; therefore preferably have with weathering resistance, water-repellancy, stain resistance, physical strength for representative, the performance of long-term reliability during for guaranteeing the outdoor exposure of solar module.In addition, in order to effectively utilize sunlight, be preferably optical loss little, the high sheet of the transparency.
As the material of solar module with face side transparent protection member, the resin molding, glass substrate etc. that are formed by vibrin, fluoro-resin, acrylic resin, cyclic olefin (being total to) polymkeric substance, vinyl-vinyl acetate copolymer etc. can be enumerated.Resin molding is preferably the vibrin, particularly pet resin of excellence in the transparency, intensity, cost etc., the fluoro-resin etc. that weathering resistance is good.As the example of fluoro-resin, there are tetrafluoroethylene-ethylene copolymer (ETFE), polyfluoroethylene resin (PVF), polyvinylidene fluoride resin (PVDF), teflon resin (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), poly-borontrifluoride ethylene chloride resin (PCTFE).From the viewpoint of weathering resistance, polyvinylidene fluoride resin is excellent, but from having weathering resistance and physical strength consideration concurrently, tetrafluoroethylene-ethylene copolymer is excellent.In addition, in order to the cementability improved with form the material sealing other layers such as sheet material layers, preferably corona treatment, Cement Composite Treated by Plasma are carried out to face side transparent protection member.In addition, also the sheet implementing stretch processing in order to improve physical strength can be used, such as biaxial stretch-formed polypropylene foil.
When as solar module with face side transparent protection member use glass substrate, the full light transmittance of wavelength 350 ~ 1400nm light of glass substrate is preferably more than 80%, is more preferably more than 90%.As above-mentioned glass substrate, general use the blank glass that the absorption in infrared portion is few, even but backboard glass, as long as to be below 3mm then few on the impact of the output characteristic of solar module for thickness.In addition, in order to improve the physical strength of glass substrate, chilled glass can be obtained by thermal treatment, but also can use without heat treated kickboard glass.In addition, in order to the sensitive surface lateral inhibition at glass substrate is reflected, the coating of antireflection can also be carried out.
(solar module rear side protects component)
Solar module solar module rear side used protects component; be not particularly limited; but owing to being positioned at the outermost layer of solar module, therefore require each characteristic such as weathering resistance, physical strength in the same manner as above-mentioned face side transparent protection member.Therefore, solar module rear side can be made up of the material same with face side transparent protection member and protect component.That is, rear side protection component also can be used as face side transparent protection member and the above-mentioned various materials that use.Especially vibrin and glass can preferably be used.In addition, rear side protection component, due to not premised on the passing through of sunlight, therefore not necessarily requires the transparency required in face side transparent protection member.Therefore, in order to strengthen the physical strength of solar module, or in order to prevent from being caused by temperature variation distortion, warpage, can reinforcement plate be puted up.Reinforcement plate preferably can use such as steel plate, plastic plate, FRP (fiberglass-reinforced plastic) plate etc.
In addition, the solar cell sealing material of present embodiment can protect component integrated with solar module rear side.By making solar cell sealing material and solar module rear side protect component integrated, the operation when module assembled, solar cell sealing material and solar module rear side protection component being cut into module size can be shortened.In addition, by making to be by the superimposed operation of integrated sheet by the operation that solar cell sealing material and solar module rear side protect component superimposed respectively, also can shorten, omitting superimposed operation.When making solar cell sealing material and solar module rear side protect component integrated, solar cell sealing material and solar module rear side protect the laminating method of component, are not particularly limited.In laminating method, be preferably known melt extruders such as using cast molding machine, extrudate piece forming machine, inflation forming machine, injection moulding machine and carry out coextrusion and obtain the method for multilayer body; Melting or another layer of heated lamination on shaping in advance one deck and obtain the method for multilayer body.
In addition, also can by employing suitable caking agent (such as, maleic anhydride modified polyolefin resin (the trade(brand)name " ADOMER (registered trademark) " of Mitsui Chemicals, Inc., the trade(brand)name " MODIC (registered trademark) " etc. of Mitsubishi Chemical Ind), unsaturated polyolefin etc. low (non-) crystallinity soft polymer, with the acrylic acid series caking agent that ethene/acrylic ester/maleic anhydride terpolymer (trade(brand)name " Bondine (registered trademark) " etc. of Zhu Hua cdF chemical company) is representative, Ethylene/vinyl acetate based copolymer, or comprise their adhesive resin composition etc.) dry lamination method or lamination methods etc. carry out lamination.
As caking agent, preferably there is the caking agent of the thermotolerance of about 120 ~ 150 DEG C, specifically, be preferably Polyester or urethane adhesive etc.In addition, in order to make the cementability of two layers improve, can at least one deck embodiment as silane system coupling processing, titanium system coupling processing, corona treatment, Cement Composite Treated by Plasma etc.
(solar cell device)
As long as solar module solar cell device used can utilize the photoelectromotive force effect of semi-conductor and the element generated electricity, be then not particularly limited.Solar cell device can use such as silicon (monocrystalline system, many crystal system, noncrystalline (amorphous) are) solar cell, compound semiconductor (III-III race, II-VI group, other) solar cell, wet type solar cell, organic semiconductor solar cell etc.Wherein, from the viewpoint of the balance etc. of power generation performance and cost, be preferably polycrystal silicon solar cell.
Silicon solar cell element, compound semiconductor solar cell device all have excellent characteristic as solar cell device, but are knownly easy to damaged because of the stress, impact etc. from outside.The solar cell sealing material of present embodiment, due to flexibility excellence, therefore absorbs the stress to solar cell device, impact etc., prevents the effect of the breakage of solar cell device large.Therefore, in the solar module of present embodiment, the layer formed by the solar cell sealing material of present embodiment preferably directly engages with solar cell device.In addition, if solar cell sealing material has thermoplasticity, even if then once after making solar module, also can take out solar cell device with comparalive ease, therefore recirculation is excellent.Form the resin combination of the solar cell sealing material of present embodiment owing to having thermoplasticity, therefore also having thermoplasticity as solar cell sealing material entirety, is also preferred from the viewpoint of recirculation.
(metal electrode)
The formation of the metal electrode that solar module is used and material, be not particularly limited, but in concrete example, have the rhythmo structure of nesa coating and metallic membrane.Nesa coating is by SnO 2, the formation such as ITO, ZnO.Metallic membrane is formed by least one metal be selected from silver, gold, copper, tin, aluminium, cadmium, zinc, mercury, chromium, molybdenum, tungsten, nickel, vanadium etc.These metallic membranes can be used alone, also can alloy as Composite and using.Nesa coating and metallic membrane are formed by methods such as CVD, sputtering, evaporations.
Solar cell device and metal electrode such as engage by the following method.First, the IPA (isopropyl alcohol) of usual well-known rosin series solder flux, water soluble flux or the aqueous solution of water are coated on surface of metal electrode.Then, carry out drying with well heater, warm braw, the solder passed into solder fusing groove has melted melts liquid, at the surface-coated solder of metal electrode.Then, reheat and solar cell device is engaged each other with metal electrode or metal electrode.
In recent years, also adopt and be directly coated with solder flux and solder at bonding station or be only coated with solder, solar cell device and metal electrode or metal electrode are carried out each other the method engaged.
(manufacture method of solar module)
The feature of the manufacture method of the solar module of present embodiment is; comprise following operation: the solar cell sealing material of the solar cell sealing material of face side transparent protection member, present embodiment, solar cell device (unit), present embodiment and rear side protection component successively lamination are formed the operation of multilayer body by (i), and (ii) by the pressurization of the multilayer body of gained and heating the operation of integration.
In operation (i), the mode preferably becoming solar cell device side with the face being formed with concaveconvex shape (embossed shapes) of solar cell sealing material configures.
In operation (ii), conventionally use vacuum laminator or thermocompressor, the multilayer body obtained is heated and pressurize and integration (sealing) in operation (i).In sealing, the solar cell sealing material of present embodiment is high due to resiliency, therefore can prevent the damage of solar cell device.In addition, because out gassing is good, therefore there is no being involved in of air yet, yield rate can manufacture the goods of high-quality well.
When manufacturing solar module, make the ethene-alpha-olefin based resin composition crosslinking curing of formation solar cell sealing material.This cross-linking process step can carry out with operation (ii) simultaneously, also can carry out after operation (ii).
When carrying out cross-linking process step after operation (ii), temperature 125 ~ 160 DEG C in operation (ii), vacuum pressure 10 to hold in the palm under following condition heating under vacuum 3 ~ 6 minutes; Then, the pressurization under the normal atmosphere of about 1 ~ 15 minute is carried out, by above-mentioned multilayer body integration.The cross-linking process step carried out after operation (ii) can be undertaken by general method, such as, the continous way of tunnel like can be used to be cross-linked stove, board-like intermittent type also can be used to be cross-linked stove.In addition, cross linking conditions is generally and carries out about 20 ~ 60 minutes at 130 ~ 155 DEG C.
On the other hand, when carrying out cross-linking process step with operation (ii) simultaneously, the Heating temperature in operation (ii) is made to be 145 ~ 170 DEG C, make be 6 ~ 30 minutes the clamping time under normal atmosphere, in addition can with operate in the same manner as carrying out the situation of cross-linking process step after operation (ii) and carry out.The solar cell sealing material of present embodiment is by having excellent crosslinking feature containing specific organo-peroxide, the bonding process through the two-stage is not needed in operation (ii), can at high temperature terminate at short notice, the cross-linking process step carried out after can being omitted in operation (ii), can improve the productivity of module significantly.
In any case; the manufacture of the solar module of present embodiment; as long as not decompose on Low molecular weight and at the temperature that the solar cell sealing material melting of present embodiment is such; temporary bond solar cell sealing material on solar cell device, protection material, then heats up and carries out the crosslinked of bonding and sealing material fully.Selection can meet the such additive formulations of each condition, such as, as long as select kind and the impregnation amount of above-mentioned linking agent and above-mentioned crosslinking coagent etc.
In addition, the above-mentioned crosslinked gel fraction preferably proceeding to the ethene-alpha-olefin copolymer after being cross-linked becomes the degree of 50 ~ 95%.Gel fraction is more preferably 50 ~ 90%, and more preferably 60 ~ 90%, most preferably be 65 ~ 90%.Calculating of gel fraction can be undertaken by following method.Such as, take the sample 1g of sealing material sheet from solar module, the Soxhlet carried out in boiling toluene extracts 10 hours.Extracting solution 30 order stainless (steel) wires are filtered, net is carried out 8 hours drying under reduced pressure at 110 DEG C.Measure the weight remaining in online remnant, the weight remaining in online remnant is set to gel fraction relative to the ratio (%) of sample size before treatment (1g).
If above-mentioned gel fraction is more than above-mentioned lower value, then the thermotolerance of solar cell sealing material becomes good, can suppress the reduction at the high strength xenon exposure experiment of the constant temperature and humid test of such as 85 DEG C × 85%RH, black dish temperature 83 DEG C, the thermal cycling test of-40 DEG C ~ 90 DEG C, the cementability in oven test.On the other hand, if gel fraction is below above-mentioned higher limit, then become the solar cell sealing material with high flexibility, the temperature tracing ability in the thermal cycling test of-40 DEG C ~ 90 DEG C improves, and therefore can prevent the generation of peeling off.
(generating set)
The excellence such as productivity, generating efficiency, life-span of the solar module of present embodiment.Therefore, employ the excellences such as the cost of the generating set of such solar module, generating efficiency, life-span, there is practical high value.Above-mentioned generating set, outdoor, indoor are all applicable to life-time service, such as, be arranged at the roof in house, utilize as the portable power source towards outdoors such as camping, the utilization etc. as the accessory power supply of automobile battery group.
Embodiment
Below, specifically describe the present invention based on embodiment, but the present invention is not limited to these embodiments.
(1) measuring method
[ethylene unit and alpha-olefin unit containing proportional]
After filtering making sample 0.35g heating for dissolving and solution glass filter (G2) of obtaining in hexachlorobutadiene 2.0ml, adding deuterated benzene 0.5ml, loading in the NMR pipe of internal diameter 10mm.Use the JNM GX-400 type NMR determinator of NEC Inc., carry out at 120 DEG C 13c-NMR measures.Cumulative number is more than 8000 times.According to gained 13c-NMR spectrum, containing of the ethylene unit in quantitative multipolymer is proportional proportional with containing of alpha-olefin unit.
[MFR]
According to ASTM D1238,190 DEG C, measure the MFR of ethene-alpha-olefin copolymer under the condition of 2.16kg loading.
[density]
According to ASTM D1505, measure the density of ethene-alpha-olefin copolymer.
[Xiao A hardness]
By ethene-alpha-olefin copolymer 190 DEG C of heating 4 minutes, after 10MPa pressurization, pressurize cooling 5 minutes until normal temperature and obtain the thick sheet of 3mm with 10MPa.Use the sheet of gained, according to ASTMD2240, measure the Xiao A hardness of ethene-alpha-olefin copolymer.
[bonding strength]
Using the transparency glass plate as face side transparent protection member used for solar batteries, the sheet sample of thickness 500 μm, the copper coin that 0.5cm is wide is coated with water soluble flux (NH-120KM, (strain) Asahi chemical research is made) and in the baking oven of 120 DEG C dry 30 minutes and be coated with the plan metallike electrode of solder, comprise the PET system tergite of silica steam plating PET, lamination is carried out according to the order of transparency glass plate/sheet sample/plan metallike electrode/sheet sample/PET system back-protective component, join vacuum laminator (NPC Inc., LM-110X160S) in, the hot plate of temperature adjustment to 150 DEG C loads and reduces pressure 3 minutes, heat 15 minutes.Then, be cross-linked 30 minutes with the baking ovens of 150 DEG C, produce the bonding strength sample of the multilayer body as transparency glass plate/sheet sample/plan metallike electrode/sheet sample/PET system back-protective component.
Along plan metallike electrode, sheet sample layer is cut into 0.5cm from this bonding strength sample wide, drawing sheet sample/PET system back-protective component, utilizes 180 degree to peel off and measures sheet sample and the bonding strength intending metallike electrode.In mensuration, employ the tensile testing machine (trade(brand)name " Instron1123 ") of Instron Inc..Utilize 180 degree of strippings, measure at 23 DEG C with 30mm, draw speed 30mm/ minute between spacing, adopt the mean value measured for 3 times.
[bonding strength after fixed temperature and humidity (DH) test]
For the multilayer body of above-mentioned gained, according to JIS C8917, utilize the constant temperature and humidity cabinet " IW241 " of Yamato scientific company, in Thoughs temperature 95 DEG C, humidity 95% condition under carry out the accelerated test of 100 hours multilayer body.
The accelerated test sample of gained is operated as described above and measures bonding strength.
[mist degree]
About mist degree, according to ASTM D1003, haze meter (NDH2000, Japanese electricity Se industrial system) is used to measure.
In addition, about sample, do not have in the scope of wavelength 350 ~ 800nm absorb territory blank sheet glass between, sandwich sheet sample, it processed under the condition same with condition when making above-mentioned bonding strength test sample and obtains multilayer body.
(2) synthesis of ethene-alpha-olefin copolymer
(synthesis example 1)
Possessing the supplying opening of successive polymerization device of internal volume 50L of agitating wing using the supply of the ratio of 8.0mmol/hr as the toluene solution of the methylaluminoxane of co-catalyst, using the supply of the ratio of 0.025mmol/hr as two (1 of Primary Catalysts, 3-dimethylcyclo-pentadienyl) the hexane slurry of zirconium dichloride, with the hexane solution of the ratio of 0.5mmol/hr supply triisobutyl aluminium, using use as catalyst solution and polymer solvent, dehydration refining after the total of the normal hexane mode that becomes 20L/hr supply continuously dehydration refining after normal hexane.Supply ethene continuously with the ratio of 3kg/hr at other supplying opening of polymerizer, supply 1-butylene with the ratio of 15kg/hr continuously, supply hydrogen continuously with the ratio of 5NL/hr simultaneously, polymerization temperature 90 DEG C, total pressure 3MPaG, carries out continuous solution polymerization under the condition of 1.0 hours residence times.Normal hexane/the toluene mixed solution of the ethene-alpha-olefin copolymer generated in polymerizer is discharged continuously via the relief outlet be arranged at bottom polymerizer, imports to chuck portion with 3 ~ 25kg/cm 2in the pipe connecting be heated by steam, become 150 ~ 190 DEG C to make the normal hexane/toluene mixed solution of ethene-alpha-olefin copolymer.
In addition, before being about to reach pipe connecting, setting up the supplying opening for injecting the methyl alcohol as catalyst deactivation agent, injecting methyl alcohol and the normal hexane/toluene mixed solution collaborated in ethene-alpha-olefin copolymer with the speed of about 0.75L/hr.At the pipe connecting inside holding of carrying vapour chuck at the normal hexane/toluene mixed solution of the ethene-alpha-olefin copolymer of about 190 DEG C, the aperture being arranged at the pressure controlled valve of pipe connecting terminal part by adjustment makes it maintain about 4.3MPaG, thus is transported to continuously in flash drum.In addition, in the transfer in flash drum, maintain about 0.1MPaG with the pressure in flash drum, the mode of the temperature maintenance about 180 DEG C in the steam portion in flash drum carries out solution temperature and the setting of pressure adjusting valve opening.Then, by by the single axle extruding machine of die temperature in 180 DEG C, with tank cooling line material, with particle dicing machine cutting line material, ethene-alpha-olefin copolymer is obtained as particle.Output is 2.2kg/hr.Physical property is shown in Table 1.
(synthesis example 2)
Respectively using the supply of the ratio of 0.012mmol/hr as the hexane solution of [dimethyl (tert-butylamides) (tetramethyl--η 5-cyclopentadienyl) silane] titanium dichloride of Primary Catalysts, using the supply of the ratio of 0.05mmol/hr as the triphenylcarbenium of co-catalyst the toluene solution of (four pentafluorophenyl groups) boric acid ester, with the hexane solution of the ratio of 0.4mmol/hr supply triisobutyl aluminium, and with the ratio of 5kg/hr supply 1-butylene, with the ratio of 100NL/hr supply hydrogen, operate in the same manner as above-mentioned synthesis example 1 in addition and obtain ethene-alpha-olefin copolymer.Output is 1.3kg/hr.Physical property is shown in Table 1.
(synthesis example 3)
Two (p-methylphenyl) methylene radical (cyclopentadienyl) respectively using the supply of the ratio of 0.003mmol/hr as Primary Catalysts (1, Isosorbide-5-Nitrae, 4,7,7,10,10-prestox-1,2,3,4,7,8,9,10-octahydro dibenzo (b, h)-fluorenyl) hexane solution of zirconium dichloride, using the supply of the ratio of 3.0mmol/hr as the toluene solution of the methylaluminoxane of co-catalyst, with the hexane solution of the ratio of 0.6mmol/hr supply triisobutyl aluminium; With the ratio of 4.3kg/hr supply ethene; Replace 1-butylene and supply 1-octene with the ratio of 6.4kg/hr; Using 1-octene and, the dehydration that uses as catalyst solution and polymer solvent refine after the total of the normal hexane mode that becomes 20L/hr supply continuously dehydration refining after normal hexane; With the ratio of 40NL/hr supply hydrogen; And make polymerization temperature be 130 DEG C, operate in the same manner as synthesis example 1 in addition and obtain ethene-alpha-olefin copolymer.Output is 4.3kg/hr.Physical property is shown in Table 1.
[table 1]
Table 1
Synthesis example 1 Synthesis example 2 Synthesis example 3
The kind of alpha-olefin 1-butylene 1-butylene 1-octene
Alpha-olefin unit containing proportional [mol%] 14 17 11
Ethylene unit containing proportional [mol%] 86 83 89
MFR [g/10 minute] 20 11 48
Shore A Hardness [-] 70 62 84
Density [g/cm <sup>3</sup>] 0.870 0.866 0.844
(3) manufacture of solar cell sealing material (sheet)
(embodiment 1)
Relative to ethene-alpha-olefin copolymer 100 weight part of synthesis example 1, 1 minute half life temperature as organo-peroxide has been coordinated to be tert-butyl hydroperoxide-2-ethylhexyl carbonate 1.0 weight part of 166 DEG C, median diameter as antacid is magnesium hydroxide 0.1 weight part of 0.1 μm, as 3-methacryloxypropyl trimethoxy silane 0.5 weight part of silane coupling agent, as cyanacrylate 1.2 weight part of crosslinking coagent, as 2-hydroxyl-4-n-octyl oxygen base benzophenone 0.4 weight part of UV light absorber, as two (2 of hindered amine system photostabilizer, 2, 6, 6-tetramethyl--4-piperidyl) sebate 0.2 weight part, as the octadecyl-3-(3 of hindered phenol system stablizer, 5-di-tert-butyl-hydroxy phenyl) propionic ester 0.05 weight part, as three (2 of phosphorus system stablizer, 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1 weight part.
At single axle extruding machine (the screw diameter 20mm φ of Thermo plastic Inc., L/D=28) the upper installation T-shaped die head of rack-style (die lip shape: 270 × 0.8mm), under the condition of die head temperature 100 DEG C, with roll temperature 30 DEG C, winding speed 1.0m/min, cooling roller uses embossing roller to carry out shaping, obtains the embossing sheet (solar cell sealing material sheet) of maximum ga(u)ge 500 μm.The voidage of the sheet of gained is 28%.The various evaluation results of the sheet of gained are shown in Table 2.
(embodiment 2 ~ 6)
Be set to the cooperation shown in table 2, in addition, operate in the same manner as the above embodiments 1 and obtain embossing sheet (solar cell sealing material sheet).The voidage of the sheet of gained is all 28%.The various evaluation results of the sheet of gained are shown in Table 2.
(comparative example 1)
Be set to the cooperation shown in table 2, in addition, operate in the same manner as the above embodiments 1 and obtain embossing sheet (solar cell sealing material sheet).The voidage of the sheet of gained is all 28%.The various evaluation results of the sheet of gained are shown in Table 2.
[table 2]
Table 2
Coordinate (weight part) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparative example 1
Ethene-alpha-olefin copolymer
Synthesis example 1 100 100
Synthesis example 2 100
Synthesis example 3 100 100 100 100
Antacid 1 0.1 0.7
Antacid 2 0.3 2.3 3.5
Antacid 3 0.5
Organo-peroxide 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Silane coupling agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Crosslinking coagent 1.2 1.2 1.2 1.2 1.2 1.2 1.2
UV light absorber 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Hindered amine system photostabilizer 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Hindered phenol system stablizer 0.05 0.05 0.05 0.05 0.05 0.05 0.05
Phosphorus system stablizer 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Evaluate
Mist degree [-] 0.9 1.5 3.7 10.5 13.3 16.5 0.6
Initial bond strenght [N/0.5cm] 21 16 16 16 14 11 19
Bonding strength [N/0.5cm] after DH test 9 12 15 16 10 11 0
Here, the antacid 1 ~ 3 of table 2 employs following antacid.
Antacid 1: magnesium hydroxide (median diameter: 0.1 μm, Sakai chemical company system, MGZ-3)
Antacid 2:Mg 0.69al 0.31(OH) 2(CO 3) 0.153.5H 2o (median diameter: 0.45 μm, Sakai chemical company system, STABIACE HT-P)
Antacid 3: magnesium hydroxide (median diameter: 1.1 μm, consonance chemical company system, KISUMA 5B)
In addition, the median diameter in the volume reference size-grade distribution of antacid uses laser diffraction formula particle size distribution device (goods name " SALD-2300 ", Inc. of Shimadzu Seisakusho Ltd.) to measure.
The application advocates that the Japanese patent application laid proposed by June 14th, 2012 is willing to the right of priority based on 2012-134646, its whole disclosure is incorporated into herein.

Claims (13)

1. a solar cell sealing material, it comprises ethene-alpha-olefin copolymer, organo-peroxide and antacid.
2. solar cell sealing material according to claim 1, described antacid comprises at least a kind in the group being selected from and being made up of magnesium hydroxide, magnesium oxide, zinc oxide, tri-lead tetroxide, calcium hydroxide, aluminium hydroxide, ironic hydroxide (II), calcium carbonate and hydrotalcite compound and/or its burned material.
3. solar cell sealing material according to claim 1 and 2, the content of the described antacid in this solar cell sealing material is 0.1 ~ 3.0 weight part relative to described ethene-alpha-olefin copolymer 100 weight part.
4. the solar cell sealing material according to any one of claims 1 to 3, described ethene-alpha-olefin copolymer meets following important document a1) ~ a4),
A1) derive from the Component units of ethene containing proportional be 80 ~ 90mol%, derive from the Component units of the alpha-olefin of carbonatoms 3 ~ 20 containing proportional be 10 ~ 20mol%,
A2) according to ASTM D1238,190 DEG C, to measure the MFR obtained under the condition of 2.16kg loading be 10 ~ 50g/10 minute,
A3) measuring according to ASTM D1505 the density obtained is 0.865 ~ 0.884g/cm 3,
A4) measuring according to ASTM D2240 the Xiao A hardness obtained is 60 ~ 85.
5. solar cell sealing material according to claim 4, according to ASTM D1238,190 DEG C, the MFR that measures the described ethene-alpha-olefin copolymer obtained under the condition of 2.16kg loading is 10 ~ 27g/10 minute.
6. the solar cell sealing material according to any one of Claims 1 to 5, the median diameter in the volume reference size-grade distribution obtained by laser diffraction and scattering formula particle size distribution method of described antacid is less than 1.0 μm.
7. the solar cell sealing material according to any one of claim 1 ~ 6, described antacid is the hydrotalcite compound shown in following general formula (A) and/or its burned material,
M 2+ 1-a·M 3+ a(OH) 2·An n- a/n·mH 2O (A)
0.2≤a≤0.35,0≤m≤5, M 2+: be selected from Mg 2+, Zn 2+, Ni 2+, Ca 2+in at least a kind of divalent metal ion, M 3+: be selected from Al 3+, Fe 3+in at least a kind of 3 valence metal ion, An:n valency negatively charged ion.
8. solar cell sealing material according to claim 7, the average plate face diameter of described hydrotalcite compound is 0.02 ~ 0.9 μm.
9. the solar cell sealing material according to any one of claim 1 ~ 8,1 minute half life temperature of described organo-peroxide is 100 ~ 170 DEG C,
The content of the described organo-peroxide in this solar cell sealing material is 0.1 ~ 3.0 weight part relative to described ethene-alpha-olefin copolymer 100 weight part.
10. the solar cell sealing material according to any one of claim 1 ~ 9, it comprises silane coupling agent further,
The content of the silane coupling agent in this solar cell sealing material is 0.1 ~ 5 weight part relative to described ethene-alpha-olefin copolymer 100 weight part.
11. solar cell sealing materials according to any one of claim 1 ~ 10, it is by by after described ethene-alpha-olefin copolymer, described organo-peroxide and described antacid melting mixing, and sheet ground extrusion moulding obtains.
12. solar cell sealing materials according to any one of claim 1 ~ 11, it is sheet.
13. 1 kinds of solar modules, it possesses:
Face side transparent protection member,
Rear side protection component,
Solar cell device, and
Sealing ply, described sealing ply makes the solar cell sealing material described in any one of claim 1 ~ 12 crosslinked and formed, and described solar cell device is sealed in described face side transparent protection member and described rear side is protected between component.
CN201380026151.8A 2012-06-14 2013-05-21 Solar cell sealing material and solar module Active CN104334631B (en)

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