CN103042786B - There is the multilayer film of polyamide and polyester layer for manufacturing the purposes of photovoltaic module - Google Patents
There is the multilayer film of polyamide and polyester layer for manufacturing the purposes of photovoltaic module Download PDFInfo
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Abstract
There is the photovoltaic module of good layer cohesive, it uses multilayer film as bonnet manufacture, described multilayer film comprises with lower floor: a) towards the polyamide moulding composition layer of solaode, c) polyester molding compounds intermediate layer, and e) polyamide moulding composition outer layer, the cohesive between the most each layer is produced 1 by selected from following method). to a) layer and/or the polyamines polyamide grafts copolymer that e) adds 0.1 to 60 wt% in layer；2). in c) layer, add the polyamines polyamide grafts copolymer of 0.1 to 30 wt%；3). introducing between a) and c) layer and/or introduce adhesion promoter layer between c) and e) layer, the moulding compound of this adhesion promoter layer comprises the polyamines polyamide grafts copolymer of 0.1 to 100 wt%.
Description
The present invention relates to the multilayer film with polyamide and polyester layer for manufacturing the purposes of solar module (solar modules).
Solar module, the most also referred to as photovoltaic module (photo voltaic module), for daylight generating and by including that the solar cell system laminate (laminate) as sandwich layer forms.This sandwich layer encapsulating material is coated with, and this encapsulating material is used as machinery and the protection of weather (weathering) relative influence.
Here, active solar cell is positioned at protecgulum (front cover) and bonnet (back
Cover) between.Protecgulum is transparent and is generally made up of glass；It combines (bonded) to the layer including solaode by means of the adhesion promoter layer (adhesion promoter layer) being generally made up of ethylene-vinyl acetate copolymer.Bonnet guarantees electric screen, and is used as the protection to climatic effect such as UV light and is used as damp-proof layer.
For bonnet, the film composite material being made up of fluoro-containing copolymer film and polyester uses currently as standard material.Fluoro-containing copolymer film in outside guarantees against weather, polyester film mechanical stability and required electrical insulating property.Another fluoro-containing copolymer film in inner side is used as the connection of the sealant with solar cell system.But, this fluoro-containing copolymer film is to the embedded material (embedding as solaode itself
Material) sealant only has low adhesion.It addition, fluoro-containing copolymer film only provides lesser degree of electric insulation, this causes needs to use thicker polyester film.
WO
2008138022 it is therefore proposed that substitute two fluoro-containing copolymer films in this composite with the film of PA-12 (PA12).In it improves, WO
2011066595 suggestions include reflective filler such as titanium dioxide towards the thermoplastic plastic layer of solaode, and the thermoplastic plastic layer (solar of solaode dorsad
Cell-remote thermoplastic layer) include the second filler such as glass fibre, wollastonite or Muscovitum, bring higher thermal conductivity for this layer.Exemplary thermoplastic is from polyamide, polyester, or polyamide and polyolefinic blend.Clearly mention PA11, PA12 and PA1010, and itself and polyolefinic blend.
But, the combination of this thermoplastic the abundant cohesive of unrealized each layer, it is to be noted that the combination of polyester and polyamide.
It is an object of the invention to provide cohesive for this purpose-promotion solution, it guarantees during the whole service life of composite, i.e. more than 20 years during, the good bond between each described layer (layers), with all of atmospheric effect (atmospheric
Effects) unrelated.
EP 1
065 048 A2 describe the multilayer materials being made up of the incompatible polyamide combined each other by adhesion promoter layer and/or polyester.Adhesion promoter layer includes the graft copolymer being made up of the polyamide chains of polyamine moieties (polyamine moiety) and grafting.
But, the document does not show that graft copolymer can be used for functional layer rather than adhesion promoter layer, and can improve the cohesive between the layer including mass filler yet.Additionally, the document is also and in the case of being not disclosed in special applications, when corresponding film is exposed to weather conditions, through the mode of years level of adhesion change.
This purpose is by using multilayer film to realize as the bonnet of photovoltaic module, and described multilayer film includes with lower floor:
A) towards the molding combination nitride layer of solaode, described moulding compound includes in every case based on this whole moulding compound at least 35
Wt%, preferably at least 40 wt%, more preferably at least 45
Wt%, particularly preferably at least 50 wt% and most preferably at least 55
The polyamide of wt% content,
C) moulding compound intermediate layer, described moulding compound includes in every case based on this whole moulding compound at least 35
Wt%, preferably at least 40 wt%, more preferably at least 45
Wt%, particularly preferably at least 50 wt% and most preferably at least 55
The thermoplastic polyester of wt% ratio, and
E) moulding compound outer layer, described moulding compound includes in every case based on whole moulding compound at least 35 wt%, preferably at least 40 wt%, more preferably at least 45 wt%, particularly preferably at least 50 wt% and the polyamide of most preferably at least 55 wt% content
A) and c) between layer and c) and e) cohesive between layer is produced by selected from following method:
1. to a) layer and/or e) adding polyamines-polyamide grafts copolymer in layer with such amount, this amount makes these layers each include based on respective moulding compound 0.1 to 60
Wt%, the most in every case 1 to 50
Wt%, and the most in every case 3 to 40
The polyamines of wt%-polyamide grafts copolymer；
2. adding polyamines-polyamide grafts copolymer in c) layer with such amount, this amount makes this layer include based on moulding compound 0.1 to 30
Wt% and preferably 1 to 20
The polyamines of wt%-polyamide grafts copolymer；
3. introducing adhesion promoter layer b) between a) and c) layer and/or introduce adhesion promoter layer d) between c) and e) layer, described adhesion promoter layer or said two adhesion promoter layer are made up of the moulding compound including following components:
I. 0.1 to 100 wt%, preferably 1 to 75 wt%, the polyamines of more preferably 3 to 50 wt% and particularly preferred 4 to 40 wt%-polyamide grafts copolymer,
II. 0 to 99.9 wt%, preferably 12.5 to 99 wt%, more preferably 25 to 97 wt% and the polyamide of particularly preferred 30 to 96 wt%,
III. 0 to 99.9 wt%, preferably 12.5 to 99 wt%, more preferably 25 to 97 wt% and the thermoplastic polyester of particularly preferred 30 to 96 wt%, and
IV. 0 to 40 wt% and preferably 0.1 to 30 wt% selected from impact-resistant modified rubber and standard auxiliary agent and the additive of mixture,
Percentage ratio is relevant with described whole moulding compound the most in every case,
Condition is that this polyamines-polyamide grafts copolymer uses following monomer to prepare:
A) based on this graft copolymer 0.5 to 25
Wt%, preferably 1 to 20
Wt%, and more preferably 1.5 to 16
Wt% has at least 4, preferably at least 8 and the polyamines of more preferably at least 11 nitrogen-atoms, and
B) polyamide-formation monomer of the combination of lactams, omega-amino carboxylic acid and/or the diamidogen of equimolar (equi molar) and dicarboxylic acids it is selected from.
Therefore, various embodiments are expected:
In the first embodiment, this multilayer film includes direct continuous print a), c) and e) layer.A) moulding compound of layer and the moulding compound of e) layer all include the polyamines according to method 1-polyamide grafts copolymer amount.
In second embodiment, this multilayer film includes direct continuous print a), c) and e) layer.C) moulding compound of layer includes the polyamines according to method 2-polyamide grafts copolymer amount.
In a third embodiment, this multilayer film includes direct continuous print a), b), c), d) and e) layer.B) and d) layer is to have the adhesion promoter layer of composition as described in method 3.
In the 4th embodiment, this multilayer film includes direct continuous print a), c), d) and e) layer.A) moulding compound of layer includes the polyamines according to method 1-polyamide grafts copolymer amount.D) layer is to have the adhesion promoter layer of composition as described in method 3.
In the 5th embodiment, this multilayer film includes direct continuous print a), b), c) and e) layer.E) moulding compound of layer includes the polyamines according to method 1-polyamide grafts copolymer amount.B) layer is to have the adhesion promoter layer of composition as described in method 3.
Except as otherwise noted, more details subsequently are equally applicable to all these embodiment.
Polyamide can be partially crystallizable polyamide, such as PA6, PA66, PA610, PA612, PA10, PA810, PA106, PA1010, PA11, PA1011, PA1012, PA1210, PA1212, PA814, PA1014, PA618, PA512, PA613, PA813, PA914, PA1015, PA11, PA12, or semiaromatic polyamide composition, referred to as polyphthalamide (PPA).(name of polyamide meets international standard, one or more numeral (first of beginning
Number (s)) give the carbon number initiateing diamidogen, one or more numerals (last number (s)) of ending give the carbon number of dicarboxylic acids.If only mentioning a numeral, it means that parent material is α, omega-amino carboxylic acid or the lactams derived by it；As for other, with reference to H.Domininghaus, Die Kunststoffe und ihre Eigenschaften [The polymers and
Their properties], page 272 and thereafter, VDI-Verlag, 1976.) suitably PPA is such as PA66/6T, PA6/6T, PA6T/MPMDT (wherein MPMD represents 2 methyl pentamethylenediamine), PA9T, PA10T, PA11T, PA12T, PA14T, and these latter type and aliphatic diamine and with aliphatic dicarboxylic acid or omega-amino carboxylic acid or the co-condensation polymer of lactams.Partially crystallizable polyamide has the melting enthalpy more than 25 J/g, according to ISO
11357, by DSC method, at second time heating steps with the integral measurement of melting peak.
Polyamide can also be semicrystalline polyamides.Semicrystalline polyamides has 4 to 25
The melting enthalpy of J/g, according to ISO 11357, by DSC method, at second time heating steps with the integral measurement of melting peak.The suitably example of semicrystalline polyamides is
Polyamide (PA PACM10 and PA of-1,10-decanedioic acid or 1,12 dodecanedioic acid and 4,4'-diamino-dicyclohexyl methane
PACM12), by have 35 to 65% trans, trans-isomer content (trans, trans
Isomer content) 4,4'-diamino-dicyclohexyl methane produce；
-copolymer based on above-mentioned partially crystallizable polyamide；With
-above-mentioned partially crystallizable polyamide and the blend of compatible amorphous polyamides.
Polyamide can also be amorphous polyamides.Amorphous polyamides has the melting enthalpy less than 4 J/g, according to ISO
11357, by DSC method, at second time heating steps with the integral measurement of melting peak.The example of amorphous polyamides is:
-p-phthalic acid and/or M-phthalic acid and 2,2,4-and 2, the polyamide of the isomer mixture of 4,4-trimethylhexane diamine,
-M-phthalic acid and 1, the polyamide of 6-hexamethylene diamine,
The mixture of-terephthalic acids/M-phthalic acid with optionally with 4, the 1 of 4'-diamino-dicyclohexyl methane mixing, the copolyamide of 6-hexamethylene diamine,
-p-phthalic acid and/or M-phthalic acid, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane and lauric lactam or the copolyamide of caprolactam,
-1,12-dodecanedioic acid or decanedioic acid, 3,3 '-dimethyl-4,4
'-diamino-dicyclohexyl methane, and (being total to) polyamide of optional lauric lactam or caprolactam,
-M-phthalic acid, 4,4'-diamino-dicyclohexyl methanes and lauric lactam or the copolyamide of caprolactam,
-1,12-dodecanedioic acid and 4, the polyamide of 4'-diamino-dicyclohexyl methane (in the case of low-antiform, trans-isomer content),
(being total to) polyamide of-p-phthalic acid and/or M-phthalic acid and optionally alkyl-substituted two (4-aminocyclohexyl) methane homologue to mix with hexamethylene diamine,
-optional two (4-amino-3-methyl-5-ethylcyclohexyl) methane together with other diamidogen, and the M-phthalic acid together with optional with other dicarboxylic acids, copolyamide,
-m-xylenedimaine and the mixture of other diamidogen such as hexamethylene diamine, and the M-phthalic acid together with optional with other dicarboxylic acids such as p-phthalic acid and/or NDA, copolyamide,
-two (4-aminocyclohexyl) methane and the mixture of two (4-amino-3-methylcyclohexyl) methane, and the copolyamide of the aliphatic dicarboxylic acid with 8 to 14 carbon atoms, and
-include the polyamide of mixture or the copolyamide of 1,14-tetracosandioic acid and aromatics, aryl aliphatic or alicyclic diamine.
These examples can change in great degree, by adding other component (such as caprolactam, lauric lactam or diamidogen/dicarboxylic acids combination) or by with other component Parts ground or fully substitute starting ingredient.
Polyamide can also be polyether ester amides or polyetheramides.Polyether ester amides is such as known by DE-A-25 23 991 and DE-A-27 12 987；They comprise PTMEG as comonomer.Polyetheramides is such as by DE-A-30
06 961 is known；They comprise polyether diamine as comonomer.
In PTMEG or polyether diamine, polyether units can be based on such as 1，2-ethandiol, 1,2-PD, 1,3-PD, BDO or 1,3 butylene glycol.Polyether units can also have the structure of mixing, such as, have the random or block distributed of the unit deriving from glycol.The weight average molecular weight of PTMEG or polyether diamine is 200 to 5000 g/ mol and preferably 400 to 3000 g/mol；Its ratio in polyether ester amides or polyetheramides is preferably 4 to 60 wt% and more preferably 10 to 50 wt%.Suitably polyether diamine can be changed by reduction amination via by corresponding PTMEG, or by being coupled to acrylonitrile, hydrogenation subsequently obtains；They can be purchased, such as with JEFFAMINE
The form of D or ED product or ELASTAMINE product is obtained by Huntsman Corp., or with Polyetheramine
The form of D series is obtained by BASF SE.If branched polyetheramides will be used, it is possible to additionally use a small amount of polyethers triamine, such as JEFFAMINE
T product.Polyether diamine or polyethers triamine are preferably used, and it is included in chain average at least 2.3 carbon atom/ether oxygen atoms.According to the present invention, polyetheramides is preferably as hydrolytic resistance is more preferable.
Useful thermoplastic polyester includes linear thermoplastic's polyester.These are carried out polycondensation prepared by glycol and dicarboxylic acids or its polyester formation derivant such as dimethyl esters.Suitably glycol has formula HO-R-OH, and wherein R is to have 2 to 40 and the branched or nonbranched aliphatic of bivalence of preferably 2 to 12 carbon atoms and/or alicyclic group.Suitably dicarboxylic acids has formula HOOC-R'-COOH, and wherein R' is to have 6 to 20 and the divalent aromatic radical of preferably 6 to 12 carbon atoms.
The example of glycol includes ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, and C36Dimer diol glycol.Glycol can be used alone or uses with the form of diol mixture.The described glycol of at most 25 mol% can be substituted by the poly alkylene glycol with below general formula
Wherein R'' is the divalent group with 2 to 4 carbon atoms, and x can take the value of 2 to 50.
The example of useful aromatic dicarboxylic acid includes p-phthalic acid, M-phthalic acid, Isosorbide-5-Nitrae-, 1,5-, 2,6-or 2,7-naphthalenedicarboxylic acid, diphenic acid and diphenyl ether 4,4'-dioctyl phthalate.At most 30
These dicarboxylic acids of mol% can be by aliphatic series or alicyclic dicarboxylic acid, such as succinic acid, adipic acid, decanedioic acid, and dodecanedioic acid or hexamethylene-Isosorbide-5-Nitrae-dioctyl phthalate substitute.
The example of suitable polyester is polyethylene terephthalate, PTT, polybutylene terephthalate (PBT), polyethylene glycol 2，6-naphthalene dicarboxylate, poly-NDA propylene glycol ester and poly-NDA butanediol ester.
The preparation of these polyester forms a part (DE-A 2,407 155,24 07 156 of prior art；Ullmanns
Encyclop die der technischen Chemie, the 4th edition, volume 19, page 65 and thereafter, Verlag Chemie, Weinheim, 1980).
The polyamines used in polyamines-polyamide grafts copolymer can following material classification:
-polyvinylamine (R mpp Chemie Lexikon, the 9th edition, volume 6, page 4921, Georg Thieme
Verlag Stuttgart 1992)
-the polyamines (polyamines) prepared by alternately polyketone
(DE-A 196 54 058)
-dendritic, such as
((H2N-(CH2)3)2N-(CH2)3)2-N(CH2)2-N((CH2)2-N((CH2)3-NH2)2)2
(DE-A-196 54 179) or
Three (2-amino-ethyl) amine, N, N-bis-(2-amino-ethyl)-N', N'-bis-[2-[two (2-amino-ethyl) amino] ethyl]-1，2-diaminoethane,
3,15-bis-(2-amino-ethyl)-6,12-bis-[2-[two (2-amino-ethyl) amino] ethyl]-9-[2-[two [2-bis-(2-amino-ethyl) amino] ethyl] amino] ethyl]-3,6,9,12,15-pentaaza heptadecane-1,17-diamidogen
(J.M. Warakomski, Chem. Mat. 1992,4,1000-1004)；
-can be by 4,5-dihydro-1, the polymerization of 3-azoles and linear polyethylene imine (Houben-Weyl, Methoden der Organischen Chemie [the Methods of Organic hydrolyzing preparation subsequently
Chemistry], E20 volume, 1482-1487 page, Georg Thieme Verlag Stuttgart, 1987)；
-can by aziridine polymerization obtain branched polyethylene imine (Houben-Weyl, Methoden der Organischen Chemie, E20 volume, 1482-1487 page, Georg Thieme Verlag Stuttgart, 1987), it is generally of following amino and is distributed:
The primary amino radical of 25 to 46%,
The secondary amino group of 30 to 45%, and
The tertiary amino of 16 to 40%.
In situations where it is preferred, this polyamines has less than 20 000 g/mol, more preferably no more than 10 000 g/mol are less than 5 000 with particularly preferred
Number-average molecular weight M of g/moln。
Lactams or omega-amino carboxylic acid as polyamide-formation monomer comprise 4 to 19, particularly 6 to 12 carbon atoms.Particularly preferably use caprolactam, omega-amino caproic acid, spicy inner formyl amine, omega-amino octanoic acid, lauric lactam, omega-amino dodecylic acid and/or omega-amino hendecanoic acid.
Diamidogen and dicarboxylic acids be combined as such as hexamethylene diamine/adipic acid, hexamethylene diamine/dodecanedioic acid, octamethylenediamine/decanedioic acid, decamethylene diamine/decanedioic acid, decamethylene diamine/dodecanedioic acid, ten dimethylene diamidogen/dodecanedioic acid and ten dimethylenes diamidogen/NDA.Additionally, it is used as other combinations all, such as decamethylene diamine/dodecanedioic acid/p-phthalic acid, hexamethylene diamine/adipic acid/p-phthalic acid, hexamethylene diamine/adipic acid/caprolactam, decamethylene diamine/dodecanedioic acid/omega-amino undecanoic acid, decamethylene diamine/dodecanedioic acid/lauric lactam, decamethylene diamine/p-phthalic acid/lauric lactam or ten dimethylenes diamidogen/NDA/lauric lactam.
In preferred embodiments, graft copolymer additionally uses selected from 0.015 to about 3
The dicarboxylic acids of mol% and 0.01 to about 1.2
Prepared by the tricarboxylic low polycarboxylic acids of mol%, in every case summation based on remaining polyamide-formation monomer.Based on this basis, these monomers are considered equivalent (equivalent) combination of diamidogen and dicarboxylic acids the most respectively.In this way, polyamide-formation monomer entirety has slight excess of carboxyl.When using dicarboxylic acids, add preferably 0.03 to 2.2 mol%, more preferably 0.05 to 1.5 mol%, more preferably 0.1 to 1 mol% and particularly 0.15 to 0.65 mol%；If use tricarboxylic acids, use preferably 0.02 to 0.9 mol%, more preferably 0.025 to 0.6 mol%, more preferably 0.03 to 0.4 mol% and particularly 0.04 to 0.25 mol%.The extra use of oligomerization carboxylic acid is obviously improved hydrolytic resistance and anti-stress cracking.
The oligomerization carboxylic acid used can be any required two-or tricarboxylic acids, such as adipic acid, suberic acid, the Azelaic Acid with 6 to 24 carbon atoms, decanedioic acid, dodecanedioic acid, M-phthalic acid, 2,6-naphthalenedicarboxylic acid, hexamethylene-Isosorbide-5-Nitrae-dioctyl phthalate, trimesic acid and/or trihemellitic acid.
Additionally, optionally, there is the aliphatic series of 3 to 50 carbon atoms, alicyclic, aromatics, aralkyl and/or the substituted monocarboxylic acid of alkylaryl, such as lauric acid, unsaturated fatty acid, acrylic acid or benzoic acid and can serve as regulator.These regulators can be used for reducing the concentration of amino, and does not change molecular skeleton.Furthermore it is possible to this method introduces the functional group of the most double or three keys etc..But it is desirable to graft copolymer has the amino of vast scale.In preferred embodiments, the amino group concentration of graft copolymer is 100 to 2500 mmol/kg, more preferably 150 to 1500 mmol/kg, particularly preferably 250 to 1300 mmol/kg and most preferably 300 to 1100 mmol/kg.Amino here represents amino end group with following should be interpreted to, but also represents any secondary or tertiary amino functional group present in this polyamines.
The graft copolymer of the present invention can be prepared by various methods.
One scheme is initially lactams or omega-amino carboxylic acid to be added together with polyamines, carries out being polymerized or polycondensation.Oligomerization carboxylic acid can add when starting or in course of reaction.
However, it is preferred to method relate to first making lactams to dissociate in the presence of water in two-step method and pre-polymerization (alternatively, the directly corresponding omega-amino carboxylic acid of use or diamidogen and dicarboxylic acids pre-polymerization)；In second step, adding polyamines, before, during or after pre-polymerization, metering adds any oligomerization carboxylic acid additionally used simultaneously.Then, mixture reduces pressure (decompress) polycondensation under the pressure of nitrogen stream or attenuating at 200 to 290 DEG C.
It is prepolymer that another preferred method relates to polyamide hydrolytic degradation, subsequently or simultaneously reacts with polyamines.Wherein end group difference is preferably used essentially a zero, or the polyamide that any oligomerization carboxylic acid wherein additionally used has been introduced by polycondensation.This oligomerization carboxylic acid can also when degradation reaction starts or during add.
These methods can be used for preparing acid number less than 40 mmol/kg, and preferably shorter than 20
Mmol/kg and the superelevation branched polyamide of more preferably less than 10 mmol/kg.Since after the response time of one to five hour of 200 DEG C to 290 DEG C, it is thus achieved that convert the most completely.
Optionally, in another method step, can be then for the vacuum stages continuing some hours.They are lasting at least four hour at 200 to 290 DEG C, preferably at least six hours and more preferably at least eight hours.After the initiation period of some hours, then observing that melt viscosity increases, this may react with each other owing to amino end group, eliminates ammonia and chain link (chain
The fact that linkage).As a result, molecular weight increases further, is particularly conducive to extrusion molding compositions.
If purpose carries out reacting to completely the most in the melt, then superelevation branched polyamide, according to prior art, it is also possible to after-condensation in solid phase (postcondensed).
A) moulding compound of layer can include the mixture of the above-mentioned polyamide of one or more of above-mentioned polyamide.Furthermore it is possible to there is total polymer content at most 40 based on moulding compound
Other thermoplastic of wt%, the most impact-resistant modified rubber or polyolefin, such as polyethylene or polypropylene.According to prior art, any rubber existed or polyolefin preferably include the functional group with its acquisition with the compatibility of polyamide substrate (matrix).Furthermore it is possible to there is common auxiliary agent and the additive, particularly light and/or heat stabilizer of polyamide, or the most reflective filler, such as titanium dioxide (WO 2011066595).In first and the 4th embodiment, it is believed that the polyamide according to claim also includes the polyamide of polyamines-polyamide grafts copolymer.
C) moulding compound of layer can include the mixture of the above-mentioned polyester of one or more of above-mentioned polyester.Furthermore it is possible to there is block polymer content at most 50 based on moulding compound in every case
Wt% and other thermoplastic of preferably up to 40 wt%, the most impact-resistant modified rubber or polyolefin, such as polyethylene or polypropylene, or in the case of second embodiment, polyamines-polyamide grafts copolymer.According to prior art, any rubber existed or polyolefin preferably include functional group；It additionally or alternatively can add bulking agent.Furthermore it is possible to there is common auxiliary agent and the additive, particularly light and/or heat stabilizer of polyester, reflective filler, such as titanium dioxide, and reinforcer, such as glass fibre, wollastonite or Muscovitum.
For the moulding compound of e) layer, identical with the moulding compound of a) layer, and for filler, identical with the moulding compound of c) layer.It addition, e) moulding compound of layer can be coloured and/or have delustering agent.
Individually film layer is generally of following thickness:
A) and e) layer: 15 to 100 μm and preferably 25 to 50 μm；
C) layer: 100 to 500 μm and preferably 150 to 400 μm；
B) and d) layer: 3 to 40 μm and preferably 5 to 25 μm.
The multilayer film used in the present invention such as can be manufactured by coextrusion lamination by all art methods.It is such as bound to wherein embed the sealant of solaode by lamination or bonding (adhesive bonding).Due to the polyamide in a) layer, in the case of lamination, obtain the good adhesive property to this sealant.The sealant used can be the normally used any material of prior art.
The present invention also provides for the photovoltaic module having used the multilayer film according to claim to manufacture.
The present invention is illustrated by the following examples.For this purpose, manufacture following moulding compound；" part " is always weight portion.
The sizing material of outer layer
(Compound)1
:
By double screw extruder (Coperion Werner & Pfleiderer ZSK 25
WLE, 36 L/D), under the barrel zone temperature of 220 DEG C, mix the VESTAMID of 79.25 parts
L1901 nf (PA12), the IRGANOX 1098 (sterically hindered phenolic antioxidant) of 0.5 part, the TINUVIN 312 (UV absorbent) and the titanium dioxide Sachtleben R 420 of 20 parts of 0.2 part.Extrudate is cooled down by water-bath and cuts off；The granule pressure air-oven at 80 DEG C (forced-air oven) subsequently is dried 12 hours.
The sizing material of outer layer
2
:
By means of double screw extruder (Coperion Werner & Pfleiderer ZSK 25
WLE, 36 L/D), under the barrel zone temperature of 220 DEG C, mix the VESTAMID L1901 of 69.25 parts
Nf, and the polyamines of 10 parts-polyamide grafts copolymer (according to EP 1 065 236 A2, by the lauric lactam of 87.063 wt%, 0.164
The dodecanedioic acid of wt%, the 50% of 8.205 wt%
Prepared by 50% hypophosphorous acid of Lupasol G 100,0.010 wt% and the deionized water of 4.558 wt%), the TINUVIN 312 of the IRGANOX of 0.5 part 1098,0.2 part and the titanium dioxide Sachtleben R 420 of 20 parts.Extrudate is cooled down by water-bath and cuts off；The granule pressure air-oven at 80 DEG C subsequently is dried 12 hours.
The sizing material in intermediate layer
3
:
By double screw extruder (Coperion Werner & Pfleiderer ZSK 25
WLE, 36 L/D), under the barrel zone temperature of 260 DEG C, mix the VESTAMID L1901 of 35.5 parts
Nf, the VESTODUR of 44.0 parts
3000 (PBT), the TEC of 20 parts
110 Kaolin, the IRGAFOS of 0.25 part
168 (processing stabilizers) and the IRGANOX 1010 (sterically hindered phenolic antioxidant) of 0.25 part.Extrudate is cooled down by water-bath and cuts off；The granule pressure air-oven at 80 DEG C subsequently is dried 12 hours.
The sizing material in intermediate layer
4
:
By double screw extruder (Coperion Werner & Pfleiderer ZSK 25
WLE, 36 L/D), under the barrel zone temperature of 260 DEG C, mix the VESTAMID L1901 of 26.5 parts, polyamines-polyamide grafts the copolymer identical with sizing material 2 of 9.0 parts, TEC 110 Kaolin of the VESTODUR of 44.0 parts 3000,20 parts, the IRGAFOS 168 and the IRGANOX 1010 of 0.25 part of 0.25 part.Extrudate is cooled down by water-bath and cuts off；The granule pressure air-oven at 80 DEG C subsequently is dried 12 hours.
The sizing material of adhesion promoter layer
5
:
By means of double screw extruder (Coperion Werner & Pfleiderer ZSK 25
WLE, 36 L/D), under the barrel zone temperature of 260 DEG C, mix the EXXELOR VA 1803 of the VESTODUR 3000,9.0 parts of 51.6 parts
(maleic anhydride-functionalized EP rubbers), the VESTAMID of 26.0 parts
ZA7295nf (PA12 extrusion type), the polyamines-polyamide grafts copolymer identical with sizing material 2 of 13.4 parts, the IRGAFOS 168 and the IRGANOX 1010 of 0.25 part of 0.25 part.Extrudate is cooled down by water-bath and cuts off；The granule pressure air-oven at 80 DEG C subsequently is dried 12 hours.
The extrusion of multilayer film:
Multilayer film system (300 from Collin
Mm slit die head, gap width 0-6 mm, the coextrusion of 3-layer or 5-tunic is for stub bar (feed block)) it is used for manufacturing three-and five-tunic (processing temperature of intermediate layer and adhesion promoter layer is about 260 DEG C, and the processing temperature of outer layer is about 230 DEG C).Layer thickness distribution sets as follows:
A/c/e:50 m/250 m/50 m
A/b/c/d/e:50 m/10 m/230 m/10 m/50 m
Result is shown in table 1.
Claims (3)
1. multilayer film includes with lower floor as the purposes of the bonnet of photovoltaic module, described multilayer film:
A) towards the molding combination nitride layer of solaode, described moulding compound comprises polyamide based on this moulding compound meter at least 35 wt% content whole, and reflective filler,
C) intermediate layer of moulding compound, described moulding compound comprises thermoplastic polyester based on this moulding compound meter at least 35 wt% ratio whole, and the filler selected from reflective filler with reinforcer, and
E) outer layer of moulding compound, described moulding compound comprises polyamide based on this moulding compound meter at least 35 wt% content whole, and the filler selected from reflective filler with reinforcer,
It is characterized in that:
A) layer and c) between layer and c) layer and e) cohesive between layer produced by selected from following method:
1). to a) layer and/or e) adding polyamines-polyamide grafts copolymer in layer with such amount, this amount makes these layer of each self-contained polyamines-polyamide grafts copolymer based on respective moulding compound meter 0.1 to 60 wt%；
2). adding polyamines-polyamide grafts copolymer in c) layer with such amount, this amount makes this layer comprise polyamines based on moulding compound meter 0.1 to 30 wt%-polyamide grafts copolymer；
3). at a) layer and c) introduce adhesion promoter layer b) between layer and/or at c) layer and e) introduce adhesion promoter layer d) between layer, described adhesion promoter layer b) and/or described adhesion promoter layer d) is made up of moulding compound, and 60 to 100 wt% of this moulding compound are composed of the following components:
I. the polyamines of 0.1 to 100 wt%-polyamide grafts copolymer,
II. the polyamide of 0 to 99.9 wt%, and
III. the thermoplastic polyester of 0 to 99.9 wt%,
Wherein I., II. are for relative this moulding compound whole with the percentage ratio of III.,
Condition is that this polyamines-polyamide grafts copolymer uses following monomer to prepare:
A) polyamines with at least 4 nitrogen-atoms based on this graft copolymer meter 0.5 to 25 wt%, and
B) polyamide forms monomer, and it is selected from the equimolar combination of lactams, omega-amino carboxylic acid and/or diamidogen with dicarboxylic acids.
Purposes the most according to claim 1, it is characterised in that:
A) layer and e) layer there is the thickness of 15 to 100 μm,
C) layer has the thickness of 100 to 500 μm, and
B) layer and d) layer there is the thickness of 3 to 40 μm.
3. use the photovoltaic module obtained according to the multilayer film in one of front claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011084518.6 | 2011-10-14 | ||
| DE201110084518 DE102011084518A1 (en) | 2011-10-14 | 2011-10-14 | Use of a multilayer film with polyamide and polyester layers for the production of photovoltaic modules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103042786A CN103042786A (en) | 2013-04-17 |
| CN103042786B true CN103042786B (en) | 2016-11-30 |
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|---|---|---|---|---|
| US6538073B1 (en) * | 1999-06-29 | 2003-03-25 | Degussa Ag | Polyamide graft copolymers |
| CN1149146C (en) * | 1999-06-29 | 2004-05-12 | 德古萨公司 | Multilayer composite material |
| CN1272381C (en) * | 2000-12-21 | 2006-08-30 | 德古萨公司 | Free-flowing polyester moulding composition |
| CN101715608A (en) * | 2007-05-10 | 2010-05-26 | 依索沃尔塔股份公司 | Use of polyamide as an encapsulating material for photovoltaic modules |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6538073B1 (en) * | 1999-06-29 | 2003-03-25 | Degussa Ag | Polyamide graft copolymers |
| CN1149146C (en) * | 1999-06-29 | 2004-05-12 | 德古萨公司 | Multilayer composite material |
| JP3860395B2 (en) * | 1999-06-29 | 2006-12-20 | デグサ アクチエンゲゼルシャフト | Thermoplastic multilayer composite and molding material |
| CN1272381C (en) * | 2000-12-21 | 2006-08-30 | 德古萨公司 | Free-flowing polyester moulding composition |
| CN101715608A (en) * | 2007-05-10 | 2010-05-26 | 依索沃尔塔股份公司 | Use of polyamide as an encapsulating material for photovoltaic modules |
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