WO2009151029A1 - Matériau d'étanchéité et module de batterie solaire dans lequel le matériau est utilisé - Google Patents

Matériau d'étanchéité et module de batterie solaire dans lequel le matériau est utilisé Download PDF

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WO2009151029A1
WO2009151029A1 PCT/JP2009/060462 JP2009060462W WO2009151029A1 WO 2009151029 A1 WO2009151029 A1 WO 2009151029A1 JP 2009060462 W JP2009060462 W JP 2009060462W WO 2009151029 A1 WO2009151029 A1 WO 2009151029A1
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group
component
sealing material
polymer
functional group
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PCT/JP2009/060462
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English (en)
Japanese (ja)
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丈夫 中村
俊之 早川
彰夫 青山
拓哉 佐野
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Jsr株式会社
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Priority to CN2009801214039A priority Critical patent/CN102057501A/zh
Priority to JP2010516849A priority patent/JPWO2009151029A1/ja
Publication of WO2009151029A1 publication Critical patent/WO2009151029A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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

Definitions

  • the present invention relates to a sealing material and a solar cell module using the same. More specifically, the present invention relates to a sealing material that is easy to form a module and is excellent in transparency, heat resistance, adhesion, and the like.
  • Solar cell modules generally protect solar cell elements such as silicon, gallium-arsenic, copper-indium-selenium with an upper transparent protective material and a lower substrate protective material, and fix the solar cell element and protective material with a sealing material. And packaged. For this reason, as a solar cell element sealing material, transparency, heat resistance, and adhesiveness with upper and lower protective materials, such as glass and a metal, are requested
  • an ethylene / vinyl acetate copolymer having a high vinyl acetate content is used from the viewpoint of flexibility and transparency. Since this material lacks heat resistance and adhesiveness, it is necessary to crosslink using an organic peroxide or a silane coupling agent. For this reason, in order to manufacture a solar cell module, a sheet of an ethylene / vinyl acetate copolymer blended with these additives is prepared and temporarily bonded to the solar cell element in a laminator over several minutes to ten and several minutes.
  • the present invention has been made in view of such problems of the prior art, and the problem is that crosslinking with an organic peroxide is not required, and thus the production efficiency of the solar cell module is remarkably increased.
  • Another object of the present invention is to provide an alternative material that can be improved and has excellent characteristics as a solar cell element sealing material.
  • the present inventors have found that the above-mentioned problems can be achieved by the sealing material shown below, and have completed the present invention. That is, according to the present invention, the following sealing materials and the like are provided.
  • component polypropylene
  • component hydrogenated diene polymer
  • component a polymer having at least one functional group selected from the following functional group X
  • a polymer (functional group-containing polymer) different from the component (ii) is used as a constituent component, the component (i) is 0 to 60 parts by mass, the component (ii) is 40 to 100 parts by mass (total amount is 100 masses).
  • Part a sealing material containing 1 to 100 parts by mass of the component (iii).
  • the component (ii) is a polymer including the following polymer block A and the following polymer block B, and at least 80% of the double bond of the following conjugated diene compound unit constituting the (ii) component is hydrogen.
  • Polymer block A Polymer block containing 50% by mass or more of an aromatic vinyl compound unit
  • Polymer block B Containing 50% by mass or more of a conjugated diene compound unit, its 1,2-bond content and 3 , 4- Polymer block in which the total content of bonds is in the range of 30-90%
  • the element sealing material of the present invention is excellent in transparency and heat resistance, and without using an organic peroxide, a silane coupling agent, or the like, with solar cell elements, upper and lower protective materials such as glass and metal, and the like. Excellent adhesiveness.
  • the sealing material of the present invention comprises (i) component: polypropylene, (ii) component: hydrogenated diene polymer, and (iii) component: a polymer having a specific functional group (functional group-containing polymer).
  • component polypropylene
  • component hydrogenated diene polymer
  • component a polymer having a specific functional group (functional group-containing polymer).
  • the component (i) is contained in an amount of 0 to 60 parts by mass
  • the component (ii) is contained in an amount of 1 to 100 parts by mass of the component (iii) with respect to 40 to 100 parts by mass (total amount 100 parts by mass).
  • each component will be described.
  • Polypropylene (component (i)) The sealing material of the present invention contains polypropylene (hereinafter sometimes referred to as “component (i)”) as a constituent component.
  • component (i) polypropylene
  • heat resistance and molding processability tend to be improved.
  • the polypropylene used in the present invention may be homopolypropylene, block polypropylene, random polypropylene, propylene / ⁇ -olefin copolymer, propylene / ethylene copolymer, propylene / butene copolymer, propylene / ethylene / butene copolymer, etc. Good.
  • the weight average molecular weight is preferably 10,000 or more, more preferably 40,000 or more, and particularly preferably 80,000 or more.
  • the "weight average molecular weight” here means the weight average molecular weight in terms of polymethyl methacrylate measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
  • the melting point of the component (i) is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 140 ° C. or higher.
  • the value measured with the differential scanning calorimeter (DSC) shall be shown.
  • a component can be manufactured by a conventionally well-known polypropylene manufacturing method. Specific examples include radical polymerization and catalytic polymerization.
  • the content of the component (i) needs to be 0 to 60 parts by mass and preferably 5 to 60 parts by mass with respect to 100 parts by mass of the total amount of the components (i) and (ii).
  • component (i) is not present, heat resistance and moldability tend to be inferior.
  • the amount exceeds 60 parts by mass the amount of the hydrogenated diene polymer (component (ii)) is small, so that it becomes hard and the sealing performance of the solar cell element is poor.
  • the sealing material of the present invention contains, in addition to polypropylene (component (i)), a hydrogenated diene polymer (hereinafter sometimes referred to as “component (ii)”) as a constituent component. (Ii) By making a component into a component, it becomes flexible and has excellent sealing properties.
  • the hydrogenated diene polymer (component (ii)) used in the present invention preferably contains a repeating unit derived from an aromatic vinyl compound and a repeating unit derived from a conjugated diene compound.
  • aromatic vinyl compound examples include styrene, tert-butyl styrene, ⁇ -methyl styrene, p-methyl styrene, p-ethyl styrene, divinyl benzene, 1,1-diphenyl styrene, vinyl naphthalene. Vinyl anthracene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like.
  • a conjugated diene polymer containing a repeating unit derived from styrene or tert-butylstyrene as a base polymer from the viewpoint of easy availability of monomers as raw materials and polymerizability.
  • conjugated diene compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1,3-octadiene. 1,3-hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene and chloroprene.
  • a conjugated diene polymer containing a repeating unit derived from 1,3-butadiene or isoprene is preferable from the viewpoint of availability of the monomer as a raw material and polymerizability.
  • the mass ratio of aromatic vinyl compound: conjugated diene compound is preferably 3:97 to 60:40.
  • the glass transition point of the component (ii) becomes too high and becomes hard and tends to have poor sealing properties.
  • Examples of the polymer including the polymer block A and the polymer block B of (ii) include (A)-(B), [(A)-(B)] x -Y, (A)-(B )-(A), [(A)-(B)-(A)] x -Y, (A)-(B)-(A)-(B), (B)-(A)-(B) -(A), [(A)-(B)-(A)-(B)] x -Y, (A)-(B)-(A)-(B)-(A) and [(A) Examples thereof include block copolymers bonded to structures such as-(B)-(A)-(B)-(A)] x -Y and [(B)-(A)] x -Y. (However, (A): Polymer block A, (B): Polymer block B, x: integer of 2 or more, Y: coupling agent residue)
  • the block copolymer containing two or more types of blocks as described above may be a tapered type or a random type in which the content of the aromatic vinyl compound or the conjugated diene compound continuously changes in the block.
  • the “coupling agent” for coupling the polymer block include methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis Halogen compounds such as (trichlorosilyl) ethane; epoxy compounds such as epoxidized soybean oil; carbonyl compounds such as diethyl adipate, dimethyl adipate, dimethyl terephthalic acid and diethyl terephthalic acid; polyvinyl compounds such as divinylbenzene; Can be mentioned.
  • the component (ii) is a polymer in which at least 80% of the double bond of the conjugated diene compound unit is hydrogenated.
  • the upper limit of the hydrogenation rate is not particularly limited, but from the viewpoint of obtaining a material excellent in weather resistance and heat resistance, a polymer in which 90% or more of the double bonds are hydrogenated is preferable. It is more preferable that the polymer is hydrogenated in an amount of at least%.
  • the component (ii) may be a polymer into which at least one functional group selected from the functional group group X is introduced.
  • a functional group By introducing a functional group, the adhesiveness with upper and lower protective materials such as glass and metal tends to be improved.
  • the component (ii) is preferably a polymer having an average of 0.01 to 100 (pieces / molecule) of the functional groups, and has an average of 0.1 to 10 (pieces / molecule). More preferably, it is a polymer. If the number of functional groups is less than 0.01 (pieces / molecule) on average, the adhesion with upper and lower protective materials such as glass and metal tends to be lowered. On the other hand, when the number of functional groups exceeds 100 (pieces / molecule), there is a possibility that a problem that molding processability deteriorates may occur.
  • the molecular weight of component (ii) is not particularly limited, but the weight average molecular weight is preferably 30,000 to 2,000,000, more preferably 40,000 to 1,000,000, and more preferably 50,000 to 500,000. Particularly preferred. If the weight average molecular weight is less than 30,000, it is not preferable because the strength and dimensional stability of the solar cell element sealing material tend to be lowered. On the other hand, if the weight average molecular weight exceeds 2,000,000, the melt viscosity of the component (ii) becomes too high, and there is a tendency for the workability and productivity of the solar cell element sealing material to decrease, which is not preferable.
  • “weight average molecular weight” means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the component can be produced, for example, by the method described in any of (a) to (e) below.
  • Production method (a) is a method in which a conjugated diene compound is obtained alone, or a conjugated diene compound and an aromatic vinyl compound are block copolymerized in the presence of an organic alkali metal compound, and the copolymer is hydrogenated. is there.
  • the resulting hydrogenated diene polymer is added to a (meth) acryloyl group-containing compound represented by the following general formula (1), an epoxy group-containing compound represented by the following general formula (2), and maleic anhydride. At least one selected from the group consisting of may be reacted in a solution or in a kneader such as an extruder.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a hydrocarbon group having 1 to 20 carbon atoms which may contain a single bond or a hetero atom
  • X 1 is an alkoxysilyl group or a hydroxyl group.
  • q represents an integer of 1 to 3 in the case of an amino group, and 1 in the case of other functional groups.
  • R 3 represents an alkenyl group having 2 to 18 carbon atoms
  • R 4 represents a carbonyloxy group, a methyleneoxy group or a phenyleneoxy group.
  • Examples of the polymer obtained by the production method (a) include (maleic anhydride-modified) styrene-ethylene / butylene-styrene block copolymer, (maleic anhydride-modified) styrene-ethylene / propylene-styrene block copolymer, (Maleic anhydride modified) styrene-ethylene / butylene / propylene / styrene block copolymer, epoxy modified styrene / ethylene / butylene / styrene block copolymer, epoxy modified styrene / ethylene / propylene / styrene block copolymer, epoxy modified Examples thereof include styrene-ethylene / butylene / propylene / styrene block copolymers.
  • the notation of (maleic anhydride-modified) styrene-ethylene / butylene-styrene block copolymer, etc. refers to styrene-ethylene / butylene-styrene block copolymer and maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer. It shall refer to both of the polymers.
  • R 5 and R 6 are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, the other is an alkyl group having 1 to 20 carbon atoms, carbon R 6 represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms, and R 7 represents an alkylene group or alkylidene group having 1 to 20 carbon atoms.
  • R 7 is an alkylene group or alkylidene group having 1 to 20 carbon atoms
  • R 8 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. Or an organosiloxy group having 1 to 100 carbon atoms.
  • Examples of the organic alkali metal compound represented by the general formula (3) or (4) include 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane, 2-lithio-1- [N, N-bis (trimethylsilyl)] aminoethane, 3-lithio-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5-tetramethyl-1- (3- Lithiopropyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-lithio-2,2-dimethyl-propyl) -1-aza-2, 5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-lithioethyl) -1-aza-2,5-disilacyclopentane, 3-lithio-1- [N- (tert -Butyl-dimethylsilyl -N- trimethylsilyl
  • R 9 and R 10 are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, the other is an alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms, and n represents an integer of 1 to 3.
  • R 9 and R 10 are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, the other is an alkyl group having 1 to 20 carbon atoms, carbon An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms, R 11 is an alkylene group or alkylidene group having 1 to 20 carbon atoms, and n is an integer of 1 to 3. Show. ]
  • Examples of the unsaturated monomer represented by the general formula (5) or (6) include p- [N, N-bis (trimethylsilyl) amino] styrene, p- [N, N-bis (trimethylsilyl) amino. Methyl] styrene, p- ⁇ 2- [N, N-bis (trimethylsilyl) amino] ethyl ⁇ styrene, m- [N, N-bis (trimethylsilyl) amino] styrene, p- (N-methyl-N-trimethylsilylamino) And styrene and p- (N-methyl-N-trimethylsilylaminomethyl) styrene.
  • Production method (d) In the production method (d), a conjugated diene compound alone or a block copolymer of a conjugated diene compound and an aromatic vinyl compound in the presence of an organic alkali metal compound is used. In this method, after the alkoxysilane compound represented by the formula (7) is reacted, the polymer is hydrogenated.
  • R 12 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. If R 12 is plural, each R 12 may be a functional group different even for the same functional group.
  • R 13 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. When there are a plurality of OR 13 s , each R 13 may be the same functional group or a different functional group.
  • R 14 represents a substituent having a polar group containing an N atom. If R 14 is plural, each R 14 may be a different functional group be the same functional group. Each R 14 may be an independent substituent or may form a cyclic structure. m and n each represents an integer of 1 to 3. However, the sum of m and n is an integer of 1 to 4. ]
  • alkoxysilane compound represented by the general formula (7) examples include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, and N, N-bis.
  • N-methyl-N-trimethylsilylaminopropyltriethoxysilane N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylmethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldi Ethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, N, N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropyldimethylethoxysilane, N , N-dimethylaminopropyldimethylmethoxysilane, N, N-dimethylaminopropylmethyldiethoxysilane, N, N-dimethylaminopropylmethyldimethoxy
  • Manufacturing method (e) In the production method (e), a conjugated diene compound is used alone, or a conjugated diene compound and an aromatic vinyl compound are block copolymerized in the presence of an organic alkali metal compound, and the resulting copolymer has an active site as an epoxy.
  • This is a method in which a compound, a ketone compound, or a nitrogen-containing compound other than the above general formulas (3) to (7) is reacted, and then the polymer is hydrogenated.
  • Epoxy compounds include ethylene oxide, propylene oxide, etc.
  • ketone compounds include acetone, benzophenone, etc.
  • nitrogen-containing compounds other than the above general formulas (3) to (7) are represented by the following general formula (8) The nitrogen-containing compound shown etc. can be mentioned.
  • R 15 and R 16 are each the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or An organosiloxy group having 1 to 100 carbon atoms
  • R 17 is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. Or an organosiloxy group having 1 to 100 carbon atoms.
  • R 15 and R 16 are each the same or different hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or An organosiloxy group having 1 to 100 carbon atoms
  • R 17 is a hydrogen atom, a trialkylsilyl
  • Examples of the nitrogen-containing compound represented by the general formula (8) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, and N-benzylideneaniline.
  • the “functional group-containing polymer” means a polymer having at least one functional group selected from the following functional group group X and different from the component (ii). . That is, a polymer in which the functional group is introduced into a polymer serving as a basic skeleton (hereinafter sometimes referred to as “base polymer”) can be used as the component (iii). By introducing such a reactive functional group, it is possible to adhere to upper and lower protective materials such as a solar cell element and glass.
  • a functional group-containing olefin polymer can be used as the functional group-containing polymer in the present invention.
  • the “functional group-containing olefin polymer” means a polymer in which an olefin polymer is used as a base polymer and the functional group is introduced into the base polymer.
  • the “olefin polymer” serving as the base polymer of the component is a polymer containing a repeating unit derived from an olefin compound (that is, ethylene and / or ⁇ -olefin). Specific examples include polymers obtained by polymerizing one or more ethylene and / or ⁇ -olefins. There is no restriction
  • the base polymer of component (iii) may include a repeating unit derived from a compound other than the olefin compound.
  • ⁇ -olefin examples include propene (hereinafter referred to as “propylene”), 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4 Examples thereof include ⁇ -olefins having 3 to 12 carbon atoms such as methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene and 1-undecene.
  • Examples of the olefin polymer include polyethylene resins, polypropylene resins, polybutene resins, methylpentene resins, etc., and one of these may be used alone or in combination of two or more. it can.
  • Examples of the “polyethylene resin” include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene / propylene copolymer, ethylene / octene copolymer, and the like.
  • polypropylene resin examples include homopolypropylene, block polypropylene, random polypropylene, propylene / ⁇ -olefin copolymer, propylene / ethylene copolymer, propylene / butene copolymer, propylene / ethylene / butene copolymer. Etc. Among these polyolefins, it is preferable to use a polyethylene resin or a polypropylene resin.
  • the component (iii) is a polymer in which at least one functional group selected from the functional group group X is introduced into the base polymer.
  • the method for introducing the functional group include a method of copolymerizing an olefin compound and a monomer having the functional group.
  • a polymer in which a carboxy group is introduced by copolymerizing ethylene and (meth) acrylic acid and a polymer in which an acid anhydride group is introduced by copolymerizing ethylene and maleic anhydride.
  • the component include ethylene / (meth) acrylic acid copolymer and ethylene / (meth) acrylic acid copolymer neutralized with a part of carboxyl group by metal ions such as Na, Zn, Mg, etc.
  • polymers having an acid anhydride group excellent in adhesiveness with upper and lower protective materials such as solar cell elements and glass are preferable, and an acid anhydride group-containing polypropylene is more compatible with the component (ii).
  • an ethylene glycidyl methacrylate copolymer is preferable.
  • a polymer into which the functional group is introduced may be used as long as the balance between mechanical properties and molding processability of the obtained sealing material is improved.
  • the polymer preferably has a functional group having an average of 0.01 to 1,000 (pieces / molecule), and preferably has an average of 0.1 to 500 (pieces / molecule). More preferred is a polymer.
  • the number of functional groups is less than 0.01 (pieces / molecule) on average, there is a tendency that good solar cell elements, upper and lower protective materials such as glass, metal, and the like cannot be obtained.
  • the average number of functional groups exceeds 1,000 (pieces / molecule), there is a risk that the fluidity of the composition is lowered and the moldability is significantly lowered.
  • the molecular weight of the component (iii) is not particularly limited, but the weight average molecular weight is preferably from 10,000 to 2,000,000, more preferably from 50,000 to 1,500,000, 1 million is particularly preferred. When the weight average molecular weight is less than 10,000, the strength of the solar cell sealing material tends to decrease. On the other hand, when the weight average molecular weight exceeds 2 million, there is a possibility that the fluidity of the composition is lowered and the moldability is lowered.
  • “weight average molecular weight” means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
  • the content of the component (iii) needs to be 0.1 to 40 parts by mass, and 0.5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (i) and (ii). Is preferred.
  • the amount is less than 0.1 parts by mass, the amount of the functional group-containing polymer is small, and the adhesiveness to upper and lower protective materials such as glass and metal tends to be lowered. If it exceeds 40 parts by mass, the amount of the functional group-containing polymer becomes excessive, and the moldability may be lowered.
  • a secondary additive other than the component (i), the component (ii), and the component (iii) can be added to the sealing material of the present invention as long as the physical properties are not impaired.
  • Secondary additives include, for example, antioxidants, ultraviolet absorbers, organic peroxides, silane coupling agents, various fillers, lubricants, plasticizers, anti-coloring agents, coloring agents, antibacterial agents, and nucleating agents. And an antistatic agent.
  • organic peroxide examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, 2,5-dimethyl- Examples thereof include 2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne.
  • dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) -3-hexyne or the like is more preferably used.
  • the amount of the organic peroxide used is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of component (i).
  • Silane coupling agents include vinyl, epoxy, styryl, methacryloxy, acryloxy, amino, ureido, chloropropyl, mercapto, sulfide, isocyanate, alkyl, and aryl groups as functional groups. Examples thereof include known silane compounds. Especially, when carrying out the graft reaction using an organic peroxide, the silane compound which has a vinyl group and a methacryloxy group as a functional group is preferable. These silane coupling agents are preferably 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the polymer.
  • antioxidant examples include phosphorus stabilizers, hindered phenol antioxidants, epoxy stabilizers, and sulfur stabilizers.
  • ultraviolet absorbers examples include benzophenone, benzotriazole, triazine, and salicylic acid ester.
  • silane coupling agent examples include compounds having a hydrolyzable group such as an alkoxy group together with an unsaturated group such as a vinyl group, an acryloxy group, and a methacryloxy group, an amino group, and an epoxy group.
  • various fillers examples include silica and mica.
  • the lubricant include fatty acid amide.
  • the sealing material sheet of the present invention can be manufactured very easily by melt-mixing the above-described components and forming a sheet.
  • the method and apparatus for mixing and molding are not particularly limited, but it is industrially advantageous and preferable to form a sheet by mixing with an extruder or a Banbury mixer, extrusion T-die molding or calendar molding.
  • the melt mixing molding temperature is preferably in the range of 150 to 250 ° C.
  • Protective material may be laminated on the sealing material sheet obtained as described above.
  • the protective material can be laminated on one side of the sealing material sheet.
  • Examples of the protective material include metals and thermoplastic resins.
  • the protective material can be laminated by pressing and coextrusion molding after the sealing material sheets are overlaid. Or you may laminate
  • the metal that can be used as the protective material may be any metal, but aluminum is preferred. These may be laminated on a protective material made of a sealing material sheet or a thermoplastic resin by vapor deposition. Further, silicon oxide or aluminum oxide may be used instead of metal.
  • thermoplastic resin that can be used as the protective material
  • any thermoplastic resin may be used.
  • polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, and acrylonitrile-styrene copolymer may be used as in the case of the sheet.
  • Polyester resins various polyamide resins such as nylon, polyimide resins, polyamideimide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethers Sulfone-based resin, polyurethane-based resin, acetal resin, may be used films or sheets of cellulose-based resin, and other various resins.
  • polyethylene terephthalate and polyvinylidene fluoride are preferred.
  • the sealing material sheet of the present invention in which the protective material as described above is laminated / not laminated can be used for a solar cell module.
  • component (ii) Prior to explaining the sealing material of the present invention, a component (ii) component [functional group-containing hydrogenated diene polymer] as a raw material was synthesized. The synthesis method is shown as a synthesis example. In addition, about the physical property value of (ii) component, it measured and evaluated with the following method.
  • Weight average molecular weight The weight average molecular weight in terms of polystyrene was determined using gel permeation chromatography (GPC, trade name: HLC-8120, manufactured by Tosoh Corporation).
  • MFR melt flow rate
  • Functional group content means the ratio of functional groups in the polymer and can be represented by the following formula (9).
  • Functional group content Functional group (individual) / Polymer (single molecular chain): (9)
  • Example 1 As component (i), 20 parts by mass of polypropylene, and as component (ii), 80 parts by mass of “ii-1” synthesized in the above [1] and component (iii) (maleic anhydride modified polypropylene; manufactured by Sanyo Chemical Industries, Product name: Umex 1010) Each 10 parts by mass was sufficiently reduced in moisture content by a vacuum dryer, then mixed, and kneaded at 230 ° C. using a 40 mm diameter extruder (Ikegai Co., Ltd.) to be pelletized.
  • the solar cell element sealing material of Example 1 was obtained as a sheet having a thickness of 0.5 mm at 230 ° C. using the obtained pellets using a T-die extruder. The evaluation results are shown in Table 2.
  • Example 2 to 7 Comparative Examples 1 to 5
  • Example 2 to 6 and Comparative Examples were the same as Example 1 except that the types and amounts of the components (i), (ii), and (iii) were changed as described in Table 2.
  • 1 to 5 solar cell element sealing materials were obtained. The results are shown in Table 2.
  • Example 8 As component (i), 40 parts by mass of polypropylene, and as component (ii), 60 parts by mass of “ii-2” synthesized in the above [1] and component (iii) (ethylene glycidyl methacrylate, trade name: Bond First CG5004, Sumitomo After 5 parts by mass of each chemical product) were sufficiently reduced in water content by a vacuum dryer, an organic oxide (dicumyl peroxide, trade name: Park Mill D, manufactured by NOF Corporation), a silane coupling agent (vinyl) Trimethoxysilane (trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed, and kneaded at 200 ° C.
  • an organic oxide dicumyl peroxide, trade name: Park Mill D, manufactured by NOF Corporation
  • a silane coupling agent (vinyl) Trimethoxysilane (trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added
  • Example 2 The solar cell element sealing material of Example 1 was obtained as a sheet having a thickness of 0.5 mm at 230 ° C. using the obtained pellets using a T-die extruder. The evaluation results are shown in Table 2.
  • Example 9 The solar cell element encapsulant of Example 9 is the same as Example 8 except that the types and amounts of the components (i), (ii), and (iii) are changed as described in Table 2. A stop material was obtained. The results are shown in Table 2.
  • Total light transmittance indicates a value measured in accordance with JIS-K7105 (light transmittance and total light reflectance). The total light transmittance was measured using a haze meter (trade name: “NDH 2000”) manufactured by Nippon Denshoku Industries Co., Ltd.
  • Adhesiveness to glass: A sheet sample having a thickness of 0.5 mm was sandwiched between transparent glass plates having a thickness of 5 mm, and a laminate was prepared by pressing the sheet sample to a thickness of 0.3 mm with a press adjusted to 200 ° C. After this laminate was cooled, the glass and sheet samples were peeled off by hand and the peel condition was observed and evaluated in the following two stages. Good: Good adhesion, bad: Adhesive failure
  • the solar cell element sealing material of Comparative Example 1 lacking the component (iii) has insufficient adhesion to glass.
  • the solar cell element sealing material of Comparative Examples 2 and 3 in which the component (i) is excessively contained has a low total light transmittance.
  • the solar cell element sealing materials of Comparative Examples 4 and 5 lacking the component (i) are displaced in the 60-degree tilt test. Also, the hardness is insufficient.
  • the sealing material and the solar cell module of the present invention are used when manufacturing a solar cell.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne un matériau d'étanchéité comportant en tant que composants structurels (i) du polypropylène, (ii) un polymère à base de diène hydrogéné, et (iii) un polymère, différent dudit composant (ii), qui est un polymère comportant au moins un type de groupe fonctionnel (un polymère contenant un groupe fonctionnel). Le matériau comprend de 1 à 100 parties en masse de composant (iii) par rapport à 100 parties en masse totale comprenant de 0 à 60 parties en masse de composant (i) et de 40 à 100 parties en masse de composant (ii).
PCT/JP2009/060462 2008-06-09 2009-06-08 Matériau d'étanchéité et module de batterie solaire dans lequel le matériau est utilisé WO2009151029A1 (fr)

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JP2010516849A JPWO2009151029A1 (ja) 2008-06-09 2009-06-08 封止材料およびそれを用いた太陽電池モジュール

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