CN111187591B - Epoxy modified polyester adhesive, solar photovoltaic back plate containing same and solar photovoltaic cell module - Google Patents
Epoxy modified polyester adhesive, solar photovoltaic back plate containing same and solar photovoltaic cell module Download PDFInfo
- Publication number
- CN111187591B CN111187591B CN202010021994.0A CN202010021994A CN111187591B CN 111187591 B CN111187591 B CN 111187591B CN 202010021994 A CN202010021994 A CN 202010021994A CN 111187591 B CN111187591 B CN 111187591B
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- China
- Prior art keywords
- modified polyester
- parts
- epoxy modified
- epoxy
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 107
- 239000000853 adhesive Substances 0.000 title claims abstract description 86
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 86
- 229920000728 polyester Polymers 0.000 title claims abstract description 77
- 229920001225 polyester resin Polymers 0.000 claims abstract description 117
- 239000004645 polyester resin Substances 0.000 claims abstract description 117
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 230000002745 absorbent Effects 0.000 claims abstract description 17
- 239000002250 absorbent Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 59
- 238000002360 preparation method Methods 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- -1 alkylene glycol Chemical compound 0.000 claims description 32
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 11
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000004224 protection Effects 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 150000001718 carbodiimides Chemical class 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 150000003873 salicylate salts Chemical class 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 6
- 238000010248 power generation Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 21
- 150000002009 diols Chemical class 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000004383 yellowing Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000007519 polyprotic acids Polymers 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
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- 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
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- 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
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Abstract
The invention provides an epoxy modified polyester adhesive, a solar photovoltaic back plate containing the same and a solar photovoltaic cell module. The epoxy modified polyester adhesive comprises the following raw materials in parts by weight: 90-110 parts of epoxy modified polyester resin, 1-20 parts of isocyanate curing agent and 0.1-5 parts of ultraviolet absorbent: the epoxy modified polyester resin comprises the following raw materials in parts by weight: 90-110 parts of polyester resin and 2-20 parts of hydrogenated epoxy resin. The epoxy modified polyester adhesive has excellent adhesive force, hydrolysis resistance, ultraviolet aging resistance and wide processing window on a base material film, and a solar backboard using the adhesive is applied to a double-sided battery assembly, so that the long-term reliable double-sided power generation efficiency can be kept.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an epoxy modified polyester adhesive, a solar photovoltaic back plate containing the epoxy modified polyester adhesive and a solar photovoltaic cell module containing the epoxy modified polyester adhesive.
Background
With the development of modern industry, global energy crisis and atmospheric pollution are increasingly prominent, traditional fuel energy is being reduced day by day, and harm to the environment is increasingly prominent, and at this time, the world is focusing on renewable energy, and the renewable energy is expected to change the energy structure of human beings and maintain long-term sustainable development, and among these, solar energy is the focus of people with its unique advantages. In recent years, the power generation efficiency of the crystalline silicon battery module is gradually improved, wherein the technical development of the double-sided power generation battery is particularly attractive, and the overall discovery efficiency of the module can be improved by 15-20% by utilizing the light on the back of the photovoltaic module. Because traditional photovoltaic backplate all is white, can't be used for two-sided battery pack, double-sided glass's subassembly can realize two-sided electricity generation, nevertheless because double-glass pack's weight is heavy, the course of working piece rate is high, a great deal of shortcoming such as the transport installation is hard, does not receive by market on a large scale. Some material manufacturers begin to research the transparent photovoltaic back plate, although the initial light transmittance is high, the transparent photovoltaic back plate is seriously yellowed under long-term outdoor line irradiation and high-temperature and high-humidity environment, the power generation efficiency of the back of the double-sided battery is seriously influenced, and the service life of the material is also doubtful.
CN109762500A discloses an adhesive for a solar photovoltaic back panel, a preparation method and application thereof, wherein the adhesive comprises saturated polyester resin, epoxy resin, a curing agent and silicate; the saturated polyester resin is prepared by reacting polybasic acid and polyhydric alcohol, wherein the polybasic acid comprises more than 20 mol% of aromatic polybasic acid and less than 80 mol% of aliphatic polybasic acid, and the polyhydric alcohol comprises more than 30 mol% of 3 polyhydric alcohols of carbon elements and less than 70 mol% of other polyhydric alcohols.
CN102250577A discloses a preparation method of a composite adhesive for solar back sheets. Belongs to the field of adhesive preparation. The adhesive for compounding the solar backboard is prepared by taking terephthalic acid, phthalic acid, ethylene glycol, 1, 6-hexanediol and cyclohexanedimethanol as raw materials, carrying out esterification reaction, carrying out polycondensation, finally adding ethyl acetate, adding a proper amount of a main agent prepared from a nano material, and mixing the main agent and a curing agent. However, since the solar cell module is mainly used outdoors, the adhesive for a solar cell back sheet has low durability and adhesiveness.
Therefore, the development of an epoxy-modified polyester adhesive that is resistant to long-term ultraviolet irradiation and has good durability and adhesion under high-temperature and high-humidity environments is the focus of current research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an epoxy modified polyester adhesive, a solar photovoltaic back plate containing the same and a solar photovoltaic cell module.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 90-110 parts of epoxy modified polyester resin, 1-20 parts of isocyanate curing agent and 0.1-5 parts of ultraviolet absorbent:
the epoxy modified polyester resin comprises the following raw materials in parts by weight: 90-110 parts of polyester resin and 2-20 parts of hydrogenated epoxy resin.
In the invention, the epoxy resin is a compound containing two or more epoxy groups (a ring consisting of one oxygen and two carbons), the epoxy groups have high activity, and are crosslinked with various curing agents to form a polymer with a net structure, so that the epoxy resin has high hardness and outstanding chemical resistance. Because hydroxyl and ether bond exist in the structure and attract the substrate, the coating has good adhesion to various substrates. The polyester resin modified by the epoxy resin can improve the adhesion of a coating film to a substrate, chemical resistance, alkali resistance and heat resistance. Under the synergistic cooperation of the epoxy modified polyester resin and the ultraviolet absorbent, the epoxy modified polyester adhesive can effectively inhibit or reduce the thermal oxidation and photo-oxidation speeds of macromolecules, remarkably improve the heat resistance and ultraviolet resistance of the material, delay the aging processes of degradation and the like of the material, and prolong the service life of a product in a high-temperature and high-humidity environment.
In the raw materials for preparing the epoxy modified polyester adhesive, the weight portion of the epoxy modified polyester resin is 90 to 110 parts, for example, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108 parts and 110 parts.
In the preparation raw materials of the epoxy modified polyester adhesive, the weight portion of the isocyanate curing agent is 1-20 parts, and can be 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts and 20 parts, for example.
In the raw material for preparing the epoxy modified polyester adhesive, the weight portion of the ultraviolet absorbent is 0.1-5 parts, and may be, for example, 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts.
In the raw materials for preparing the epoxy modified polyester resin, the weight portion of the polyester resin is 90-110 parts, for example, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108 parts and 110 parts.
In the raw materials for preparing the epoxy modified polyester resin, the hydrogenated epoxy resin is 2 to 20 parts by weight, for example, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, and 20 parts.
Preferably, the raw materials for preparing the polyester resin comprise dibasic acid, dihydric alcohol and a catalyst.
Preferably, the molar mass ratio of the dibasic acid, the dibasic alcohol and the catalyst is (1-1.2): (1-1.2): (0.01-0.05), and may be, for example, 1:1:0.01, 1:1:0.02, 1:1:0.03, 1:1:0.04, 1:1:0.05, 1:1.2:0.01, 1:2.1:0.02, 1:1.2:0.03, 1:1.2:0.04, 1:1.2:0.05, 1.2:1:0.01, 1.2:1:0.02, 1.2:1:0.03, 1.2:1:0.04, 1.2:1: 0.05.
Preferably, the dibasic acid is a mixture of an aromatic dibasic acid and an aliphatic dibasic acid.
Preferably, the aromatic dibasic acid is contained in a molar percentage of 70 mol% or less, for example, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, based on 100 mol% of the total molar mass of the dibasic acid. The saturated polyester resin of the present invention is polymerized from polybasic acid and polyhydric alcohol. When the aromatic polybasic acid is more than 70 mol% of the dibasic acid, the pressure-sensitive adhesive layer is poor in ultraviolet resistance and is likely to be yellowed.
Preferably, the aromatic dibasic acid comprises any one of terephthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride or trimellitic anhydride or a combination of at least two thereof.
Preferably, the aliphatic dibasic acid comprises any one of adipic acid, sebacic acid, or 1, 4-cyclohexanedicarboxylic acid, or a combination of at least two thereof.
Preferably, the diol is C3-C20 alkylene glycol, or a mixture of C3-C20 alkylene glycol and C1-C2 alkylene glycol (the diol may be C3-C20 alkylene glycol, and the diol may also be a mixture of C3-C20 alkylene glycol and C1-C2 alkylene glycol);
preferably, the diol is a mixture of C3-C20 alkylene glycols (which may be C3 alkylene glycols, C5 alkylene glycols, C7 alkylene glycols, C10 alkylene glycols, C12 alkylene glycols, C14 alkylene glycols, C16 alkylene glycols, C18 alkylene glycols, C20 alkylene glycols, for example) and C1-C2 alkylene glycols (which may be C1 alkylene glycols and C2 alkylene glycols, for example).
The molar mass of the C3-C20 alkylene glycol is preferably 50 mol% or more, for example, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, based on 100 mol% of the total molar mass of the diols. In the dihydric alcohol, if the C3-C20 alkylene glycol is less than 50 mol%, the hydrolysis resistance of the adhesive layer is poor.
Preferably, the C3-C20 alkylene glycol includes any one or a combination of at least two of 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-2-ethyl-1, 3-propanediol, or 1, 4-cyclohexanedimethanol;
preferably, the C1-C2 alkylene glycol includes methyl glycol and/or ethylene glycol.
Preferably, the catalyst is antimony trioxide.
Preferably, the hydrogenated epoxy resin is a hydrogenated aliphatic epoxy resin.
Preferably, the preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: mixing and stirring dibasic acid, dibasic alcohol and a catalyst, and reacting to obtain the polyester resin;
(2) epoxy modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring, and reacting to obtain the epoxy modified polyester resin.
Preferably, step (1) is carried out in a stainless steel reaction vessel equipped with a stirrer, a cooling tube and a thermometer.
Preferably, step (1) is carried out under nitrogen protection.
Preferably, the temperature of the mixing and stirring in step (1) is 160-240 ℃, for example 160 ℃, 180 ℃, 200 ℃, 220 ℃ and 240 ℃.
Preferably, the mixing and stirring time in the step (1) is 3-5h, for example, 3h, 3.5h, 4h, 4.5h, 5 h.
Preferably, the step (1) of mixing and stirring further comprises a temperature-rising reaction.
Preferably, the temperature of the temperature raising reaction is 260-270 ℃, for example, 260 ℃, 262 ℃, 264 ℃, 266 ℃, 268 ℃ and 270 ℃.
Preferably, the pressure of the temperature-raising reaction is 50Pa or less, and may be, for example, 0Pa, 5Pa, 10Pa, 15Pa, 20Pa, 22Pa, 24Pa, 26Pa, 28Pa, 30Pa, 32Pa, 34Pa, 36Pa, 38Pa, or 40 Pa.
Preferably, the time for the temperature-raising reaction is 2 to 4 hours, and may be, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, or 4 hours.
Preferably, the temperature of the mixing and stirring in step (2) is 230-240 ℃, for example 230 ℃, 232 ℃, 234 ℃, 236 ℃, 238 ℃ and 240 ℃.
Preferably, the mixing and stirring time of the step (2) is 2-5h, for example, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5 h.
Preferably, the epoxy-modified polyester resin has an intrinsic viscosity of 0.3 to 0.8dl/g, and may be, for example, 0.3dl/g, 0.35dl/g, 0.4dl/g, 0.45dl/g, 0.5dl/g, 0.55dl/g, 0.6dl/g, 0.65dl/g, 0.7dl/g, 0.75dl/g, 0.8 dl/g.
Preferably, the acid value of the epoxy-modified polyester resin is 1mg KOH/g or less, and may be, for example, 0.1mg KOH/g, 0.2mg KOH/g, 0.3mg KOH/g, 0.4mg KOH/g, 0.5mg KOH/g, 0.6mg KOH/g, 0.7mg KOH/g, 0.8mg KOH/g, 0.9mg KOH/g, or 1mg KOH/g.
Preferably, the epoxy-modified polyester adhesive has a degree of crosslinking of 40% or more, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%.
Preferably, the isocyanate curing agent is a reactive isocyanate curing agent and/or a blocked isocyanate curing agent;
preferably, the reactive isocyanate curing agent includes any one or a combination of at least two of hexamethylene diisocyanate, hexamethylene diisocyanate dimer, hexamethylene diisocyanate trimer, isophorone diisocyanate dimer, isophorone diisocyanate trimer, xylylene diisocyanate dimer or xylylene diisocyanate trimer, preferably any one or a combination of at least two of hexamethylene diisocyanate, hexamethylene diisocyanate dimer or hexamethylene diisocyanate trimer.
Preferably, the reactive isocyanate curing agent is any one or a combination of at least two of N3300 of germany bayer, N3390 of germany bayer, TPA90SB of japan asahi, TPA100 of japan asahi, or HT-100 of nicotinaldehyde.
Preferably, the blocked isocyanate curing agent comprises any one of phenol, polyether glycol or methyl ethyl ketoxime or a combination of at least two of the above.
Preferably, the ultraviolet absorber comprises any one of o-hydroxybenzophenones, benzotriazoles, salicylates, triazines, or substituted acrylonitriles or a combination of at least two thereof.
Preferably, the ultraviolet absorber comprises suwei
UV-5411, Suwei
A430 of Taiwan double bond
1260. UV-2908 for new debye materials or UV3529 for new debye materials.
Preferably, the raw materials for preparing the epoxy modified polyester adhesive also comprise 1-3 parts of a carbodiimide hydrolysis resistance auxiliary agent, such as 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts and 3 parts.
Preferably, the hydrolysis resistance auxiliary agent of the carbodiimide type is monocarbodiimide and/or polycarbodiimide;
preferably, the monocarbodiimide is any one of dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or a combination of at least two thereof.
In a second aspect, the invention provides a solar photovoltaic back panel, which comprises a fluorocarbon resin layer, a polyester insulating film layer, an adhesive layer and a weather-resistant film layer, which are sequentially stacked, wherein the adhesive layer is prepared from the epoxy modified polyester adhesive in the first aspect.
Preferably, the raw material for preparing the fluorocarbon resin layer is fluorocarbon resin containing hydroxyl.
Preferably, the hydroxyl-containing fluorocarbon resin comprises any one of or a combination of at least two of tetrafluoroethylene/vinyl ether copolymer, tetrafluoroethylene/vinyl ether monomer copolymer, chlorotrifluoroethylene and vinyl ester copolymer, chlorotrifluoroethylene and vinyl ether copolymer, or polyvinylidene fluoride.
Preferably, the polyester insulating film layer is a polyethylene terephthalate film (PET film).
Preferably, the weather-resistant film layer includes any one of a polyvinyl fluoride film (PVF film), a polyvinylidene fluoride film (PVDF film), a tetrafluoroethylene and ethylene copolymer film (ETFE film), a weather-resistant polyethylene terephthalate film (PET film), or a combination of at least two thereof.
Preferably, the thickness of the fluorocarbon resin layer is 1 to 10 μm, and may be, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm.
Preferably, the thickness of the polyester insulating film layer is 200-300 μm, such as 200 μm, 220 μm, 240 μm, 260 μm, 280 μm, 300 μm.
Preferably, the thickness of the adhesive layer is 5-15 μm, e.g., 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm.
Preferably, the weatherable film layer has a thickness of 10 to 50 μm, and may be, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm.
In a third aspect, the invention provides a solar photovoltaic cell module comprising the solar photovoltaic back sheet according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
the epoxy modified polyester adhesive has excellent adhesive force to a base material film, hydrolysis resistance, low yellowing index after ultraviolet aging resistance and wide processing window, and a solar backboard using the adhesive is applied to a double-sided battery assembly, so that the long-term reliable double-sided power generation efficiency can be maintained.
Drawings
Fig. 1 is a schematic structural diagram of the solar photovoltaic back panel of the present invention.
Wherein, 1 is a fluorocarbon resin layer, 2 is a polyester insulating film layer, 3 is an adhesive layer, and 4 is a weather-resistant film layer.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, 10 parts of isocyanate curing agent (TPA100) and 2 parts of ultraviolet absorbent (UV 5411).
The epoxy modified polyester resin comprises the following raw materials in parts by weight: 100 parts of polyester resin and 5 parts of hydrogenated epoxy resin (ST 3000).
The preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, wherein the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 59 mol% of isophthalic acid, 40 mol% of sebacic acid and 1 mol% of trimellitic anhydride, based on the total molar mass of the dibasic acid taken as 100 mol%; the diols comprise 52 mol% of 1, 6-hexanediol, 20 mol% of neopentyl glycol and 28 mol% of 1, 4-cyclohexanedimethanol, based on the total molar mass of the diols being 100 mol%.
The preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: in a stainless steel reaction kettle with a stirrer, a cooling pipe and a thermometer, mixing and stirring dibasic acid, dibasic alcohol and a catalyst for 3 hours at 200 ℃ under the protection of nitrogen, then releasing the pressure in the reaction kettle, reducing the pressure in the reaction kettle to 650Pa after 1 hour, continuously heating the reaction kettle to 265 ℃, continuously reducing the pressure in the reaction kettle to 40Pa, preserving the heat for 3 hours in an environment of 265 ℃ and below 40Pa, and reacting to obtain the polyester resin;
(2) epoxy modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 4h at 230 ℃, and reacting to obtain the epoxy modified polyester resin.
The preparation method of the epoxy modified polyester adhesive comprises the following steps: and mixing and stirring the epoxy modified polyester resin, the isocyanate curing agent and the ultraviolet absorbent to obtain the epoxy modified polyester adhesive.
Example 2
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, 12 parts of isocyanate curing agent (N3300) and 3 parts of ultraviolet absorber (A430).
The epoxy modified polyester resin comprises the following raw materials in parts by weight: 100 parts of polyester resin and 5 parts of hydrogenated epoxy resin (ST 3000).
The preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, wherein the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 32 mol% of terephthalic acid, 18 mol% of isophthalic acid, 30 mol% of adipic acid and 20 mol% of 1, 4-cyclohexanedicarboxylic acid, based on the total molar mass of the dibasic acid taken as 100 mol%; the diols comprise 15 mol% of 2-methyl-1, 3-propanediol, 20 mol% of 1, 3-propanediol and 65 mol% of 1, 6-hexanediol, based on the total molar mass of the diols being 100 mol%.
The preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: in a stainless steel reaction kettle with a stirrer, a cooling pipe and a thermometer, mixing and stirring dibasic acid, dibasic alcohol and a catalyst for 5 hours at 160 ℃ under the protection of nitrogen, then releasing the pressure in the reaction kettle, reducing the pressure in the reaction kettle to 650Pa after 1 hour, continuously heating the reaction kettle to 265 ℃, continuously reducing the pressure in the reaction kettle to 30Pa, and preserving the temperature for 3 hours under the environment of 265 ℃ and 30Pa to obtain the polyester resin;
(2) epoxy-modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 4h at 230 ℃, and reacting to obtain the epoxy modified polyester resin.
The preparation method of the epoxy modified polyester adhesive comprises the following steps: and mixing and stirring the epoxy modified polyester resin, the isocyanate curing agent and the ultraviolet absorbent to obtain the epoxy modified polyester adhesive.
Example 3
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, isocyanate curing agent (TPA90SB10 parts and ultraviolet absorbent: (
1260) And 2 parts.
The epoxy modified polyester resin comprises the following raw materials in parts by weight: 100 parts of polyester resin and 5 parts of hydrogenated epoxy resin (ST 3000).
The preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, wherein the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 50 mol% of isophthalic acid, 25 mol% of phthalic acid and 25 mol% of sebacic acid, based on 100 mol% of the total molar mass of the dibasic acid; the diols comprise 20 mol% of 1, 6-hexanediol and 80 mol% of neopentyl glycol, based on the total molar mass of the diols being 100 mol%.
The preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: in a stainless steel reaction kettle with a stirrer, a cooling pipe and a thermometer, mixing and stirring dibasic acid, dibasic alcohol and a catalyst at 240 ℃ for 3 hours under the protection of nitrogen, then releasing the pressure in the reaction kettle, reducing the pressure in the reaction kettle to 650Pa after 1 hour, continuously heating the reaction kettle to 265 ℃, continuously reducing the pressure in the reaction kettle to 20Pa, and preserving the temperature for 3 hours under the environment of 265 ℃ and 20Pa to obtain the polyester resin;
(2) epoxy modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 5 hours at 230 ℃, and reacting to obtain the epoxy modified polyester resin.
The preparation method of the epoxy modified polyester adhesive comprises the following steps: and mixing and stirring the epoxy modified polyester resin, the isocyanate curing agent and the ultraviolet absorbent to obtain the epoxy modified polyester adhesive.
Example 4
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, 10 parts of isocyanate curing agent (TPA100) and 2 parts of ultraviolet absorbent (UV 5411).
The epoxy modified polyester resin comprises the following raw materials in parts by weight: 100 parts of polyester resin and 5 parts of hydrogenated epoxy resin (ST 3000).
The preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, wherein the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 50 mol% of isophthalic acid, 25 mol% of adipic acid, 24 mol% of sebacic acid and 1 mol% of trimellitic anhydride, wherein the total molar mass of the dibasic acid is 100 mol%; the diols comprise 20 mol% of 2-methyl-1, 3-propanediol, 40 mol% of 1, 6-hexanediol and 40 mol% of neopentyl glycol, based on the total molar mass of the diols being 100 mol%.
The preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: in a stainless steel reaction kettle with a stirrer, a cooling pipe and a thermometer, mixing and stirring dibasic acid, dibasic alcohol and a catalyst at 200 ℃ for 3 hours under the protection of nitrogen, then releasing the pressure in the reaction kettle, reducing the pressure in the reaction kettle to 650Pa after 1 hour, continuously heating the reaction kettle to 265 ℃, continuously reducing the pressure in the reaction kettle to 40Pa, and preserving the temperature for 3 hours under the environment of 265 ℃ and 40Pa to obtain the polyester resin;
(2) epoxy modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 4h at 230 ℃, and reacting to obtain the epoxy modified polyester resin.
The preparation method of the epoxy modified polyester adhesive comprises the following steps: and mixing and stirring the epoxy modified polyester resin, the isocyanate curing agent and the ultraviolet absorbent to obtain the epoxy modified polyester adhesive.
Example 5
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, 10 parts of isocyanate curing agent (TPA100) and 2 parts of ultraviolet absorbent (UV 5411).
The epoxy modified polyester resin comprises the following raw materials in parts by weight: 100 parts of polyester resin and 5 parts of hydrogenated epoxy resin (ST 3000).
The preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, wherein the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 40 mol% of isophthalic acid, 20 mol% of adipic acid and 20 mol% of sebacic acid, based on 100 mol% of the total molar mass of the dibasic acid; the dihydric alcohol comprises 50mol percent of 1, 4-butanediol, 20mol percent of 1, 5-pentanediol and 30mol percent of 1, 6-hexanediol based on the total molar mass of the dihydric alcohol being 100mol percent.
The preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: in a stainless steel reaction kettle with a stirrer, a cooling pipe and a thermometer, mixing and stirring dibasic acid, dibasic alcohol and a catalyst for 3 hours at 200 ℃ under the protection of nitrogen, then releasing the pressure in the reaction kettle, reducing the pressure in the reaction kettle to 650Pa after 1 hour, continuously heating the reaction kettle to 265 ℃, continuously reducing the pressure in the reaction kettle to 40Pa, preserving the heat for 3 hours in an environment of 265 ℃ and below 40Pa, and reacting to obtain the polyester resin;
(2) epoxy modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 4h at 230 ℃, and reacting to obtain the epoxy modified polyester resin.
The preparation method of the epoxy modified polyester adhesive comprises the following steps: and mixing and stirring the epoxy modified polyester resin, the isocyanate curing agent and the ultraviolet absorbent to obtain the epoxy modified polyester adhesive.
Example 6
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, 10 parts of isocyanate curing agent (TPA100) and 2 parts of ultraviolet absorbent (UV 5411).
The epoxy modified polyester resin comprises the following raw materials in parts by weight: 100 parts of polyester resin and 5 parts of hydrogenated epoxy resin (ST 3000).
The preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, wherein the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 40 mol% of isophthalic acid, 20 mol% of adipic acid and 20 mol% of sebacic acid, wherein the total molar mass of the dibasic acid is 100 mol%; the dihydric alcohol comprises 50mol percent of 1, 4-butanediol, 40mol percent of 1, 5-pentanediol and 10mol percent of ethylene glycol based on the total molar mass of the dihydric alcohol being 100mol percent.
The preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: in a stainless steel reaction kettle with a stirrer, a cooling pipe and a thermometer, mixing and stirring dibasic acid, dibasic alcohol and a catalyst at 200 ℃ for 3 hours under the protection of nitrogen, then releasing the pressure in the reaction kettle, reducing the pressure in the reaction kettle to 650Pa after 1 hour, continuously heating the reaction kettle to 265 ℃, continuously reducing the pressure in the reaction kettle to 40Pa, and preserving the temperature for 3 hours under the environment of 265 ℃ and 40Pa to obtain the polyester resin;
(2) epoxy modified polyester resin: and (2) adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 4h at 230 ℃, and reacting to obtain the epoxy modified polyester resin.
The preparation method of the epoxy modified polyester adhesive comprises the following steps: and mixing and stirring the epoxy modified polyester resin, the isocyanate curing agent and the ultraviolet absorbent to obtain the epoxy modified polyester adhesive.
Example 7
The embodiment provides an epoxy modified polyester adhesive, which comprises the following raw materials in parts by weight: 100 parts of epoxy modified polyester resin, 10 parts of isocyanate curing agent (TPA100), 2 parts of ultraviolet absorbent (UV5411) and 2 parts of carbodiimide type hydrolysis-resistant additive (Rhine chemical P200), wherein the component contents and the preparation method of the epoxy modified polyester resin are the same as those in example 1.
Example 8
This example provides an epoxy modified polyester adhesive, which is different from example 1 only in that the content of the hydrogenated epoxy resin (ST3000) is reduced to 2 parts, and the content of other components and the preparation method are not changed.
Example 9
This example provides an epoxy modified polyester adhesive, which differs from example 1 only in that the content of the hydrogenated epoxy resin (ST3000) is increased to 20 parts, and the content of other components and the preparation method are not changed.
Comparative example 1
This comparative example provides a polyester adhesive differing from example 1 only in that: the epoxy-modified polyester resin was replaced with the polyester resin prepared in example 1, and the contents of other components and the preparation method were the same as in example 1.
Comparative example 2
This comparative example provides a polyester adhesive differing from example 1 only in that: the epoxy-modified polyester resin was replaced with the polyester resin prepared in example 1, and the content of the curing agent (TPA100) was increased to 24 parts, and the contents of other components and the preparation method were the same as in example 1.
Comparative example 3
This comparative example provides a polyester adhesive differing from example 1 only in that: the contents of other components and the preparation method were the same as in example 1 without adding an ultraviolet absorber.
Comparative example 4
This comparative example provides a polyester adhesive differing from example 1 only in that: the epoxy-modified polyester resin was replaced with the polyester resin prepared in example 1, without adding an ultraviolet absorber, and the contents of other components and the preparation method were the same as those of example 1.
Comparative example 5
This comparative example provides a polyester adhesive differing from example 1 only in that: the epoxy-modified polyester resin was replaced with the polyester resin prepared in example 1, and the content of the curing agent (TPA100) was reduced to 1.8 parts, and the contents of other components and the preparation method were the same as in example 1.
Comparative example 6
This comparative example provides an epoxy modified polyester adhesive differing from example 1 only in that: the preparation raw materials of the polyester resin are different, the preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and antimony trioxide, and the molar mass ratio of the dibasic acid to the dihydric alcohol to the antimony trioxide is 1:1: 0.4; the dibasic acid comprises 40mol percent of terephthalic acid and 60mol percent of isophthalic acid based on the total molar mass of the dibasic acid being 100mol percent; the diol comprises 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol based on 100 mol% of the total molar mass of the diol, and the contents of other components and the preparation method are the same as those in example 1.
Test example 1
The epoxy-modified polyester resins and epoxy-modified polyester adhesives prepared in examples 1-6 and comparative example 6, respectively, were tested for basic performance parameters as follows:
(1) determination of the glass transition temperature Tg Point:
weighing 10mg of a resin sample to be tested, and testing by using a DSC differential scanning calorimeter (German relaxation-resistant DSC200F3), wherein the scanning temperature interval is-50-100 ℃, and the heating rate is 20K/min.
(2) Determination of limiting viscosity:
phenol and 1,1,2, 2-tetrachloroethane are prepared into a mixed solvent according to the mass ratio of 60:40, 0.1g of a resin sample to be tested is dissolved in 25mL of the mixed solvent, the reduced viscosity is tested by an Ubbelohde viscometer at 30 ℃, then a relation curve graph of the reduced viscosity and the concentration is measured by a method of diluting the concentration, and the ultimate viscosity when the concentration is 0 is calculated.
(3) Measurement of acid value:
weighing 0.5g of a resin sample to be detected, putting the resin sample into a100 mL triangular conical flask, adding 20-30 mL of chloroform solution, shaking up to completely dissolve the sample, adding 2-3 drops of phenolphthalein indicator, titrating the solution to pink by using 0.01mol/L potassium hydroxide standard solution, and keeping the solution not to fade for 15s as an end point.
The acid value was calculated by the following formula, and the acid value (AV, mg KOH/g) of the sample
Wherein, V1Represents the volume (mL) of the potassium hydroxide standard solution consumed by the sample, C represents the concentration (mol/L) of the potassium hydroxide standard solution, and W represents the mass (g) of the sample.
The specific test results are shown in table 1:
TABLE 1
As is clear from the above test data, the epoxy-modified polyester resins specified in examples 1 to 5 had glass transition temperatures Tg of-20 to 16 ℃, limiting viscosities of 0.39 to 0.48dl/g and acid numbers of 0.21 to 0.36mg KOH/g. The polyester resin disclosed by the invention is moderate in limiting viscosity, can effectively ensure the cohesive force and heat resistance of an adhesive layer, and can ensure the coating of the adhesive.
Test example 2
Measurement of the degree of crosslinking of epoxy-modified polyester adhesives
Determination of the degree of crosslinking: the epoxy modified polyester adhesive is baked for 5 minutes at 80 ℃, and then is subjected to curing and crosslinking reaction at 60 ℃ for 3 days to form a glue film. Weighing the adhesive film1Sealing and wrapping the glue film by using a 200-mesh steel wire mesh and weighing W2Then the mixture is soaked in ethyl acetate solution for 24 hours, taken out and dried at 100 ℃ for 5 minutes, and weighed and recorded as W3. Degree of crosslinking ═ W2-W3)*100％/W1The specific test results are shown in table 2:
TABLE 2
| Sample to be tested | Degree of crosslinking (%) |
| Example 1 | 95 |
| Example 2 | 95 |
| Example 3 | 95 |
| Example 4 | 95 |
| Example 5 | 95 |
| Example 6 | 95 |
| Example 7 | 95 |
| Example 8 | 95 |
| Example 9 | 95 |
| Comparative example 1 | 95 |
| Comparative example 2 | 100 |
| Comparative example 3 | 95 |
| Comparative example 4 | 95 |
| Comparative example 5 | 35 |
| Comparative example 6 | 95 |
From the above test data, it can be seen that the polyester adhesives prepared in examples 1 to 9 have a degree of crosslinking of 95% or more, an increased degree of crosslinking, improved structural stability of the epoxy-modified polyester adhesive, and contribute to increase the cohesion and heat resistance of the epoxy-modified polyester adhesive.
Test example 3
Preparation and performance test of solar photovoltaic back panel
(1) Preparation of solar photovoltaic back plate
Weighing 100 parts of fluorocarbon resin GK570 (Japan Dajin chemical), 0.5 part of coupling agent KBM403 (Japan shin-Etsu chemical) and 50 parts of butyl acetate solvent, stirring at high speed for 800 r/min, then adding 15 parts of curing agent TPA100 (Asahi chemical Co., Ltd.), stirring for 30min, coating on a PET polyester insulating film layer to a thickness of 5 μm, and baking at 150 ℃ for 5min to obtain a PET polyester insulating film layer with a thickness of 250 μm.
The adhesives prepared in examples 1 to 9 and the adhesives prepared in comparative examples 1 to 6 were uniformly coated on the upper surface of the backing sheet, and the adhesive layer of 10 μm was uniformly coated on the other side (the side not coated with fluorocarbon resin) of the PET film, and the solvent was evaporated by heating at a heating rate of 100 ℃/5min, and the PVDF film and the adhesive layer were thermally pressed and compounded at a temperature of 90 ℃ to a thickness of 25 μm, and then cured at 60 ℃ for 3 days to prepare a backing sheet.
(2) Performance testing
The performance evaluations were performed on the backsheets made from the adhesives prepared in examples 1-9 above and the adhesives prepared in comparative examples 1-6, respectively, wherein each of the backsheets performance test methods is as follows:
testing the peeling force:
cutting the above back sheet sample into 1cm × 20cm samples, peeling off the fluorine film and the polyester film, testing the peeling force at 180 deg.C, peeling rate of 100mm/min, and using Shimadzu tensile machine, model AGS-1 KN.
Cold and hot circulation resistance
Placing the backboard sample into an environment box, setting the conditions of-40-85 ℃/100 cycles, keeping the temperature at-40 ℃/constant for 1 hour, raising the temperature at-40 ℃ to 85 ℃/0.5 hour, keeping the temperature at 85 ℃/constant for 1 hour, and lowering the temperature at-40 ℃/0.5 hour to 3 hours for one cycle.
The back plate after cold and hot impact has no bubbles, delaminating, cracking, fluorine film shrinking and yellowing, which are OK, or NG.
(iii) resistance to wet heat aging
And (3) putting the back plate sample into an environment box, setting the conditions of 85 ℃ and 85% RH, continuously operating for 2000 hours, wherein the back plate is OK when the damp and hot aging is carried out and has no bubble, delamination and cracking, and the fluorine film is shrunk and yellowed, otherwise, NG.
(iv) visible light transmittance
After UV aging of 200KWh, a ring-shaped ultraviolet spectrophotometer (Shimadzu Japan) is used, and the visible light wave band is 400-1100 cm-1Test light transmittance within the range.
Measurement of yellowing index
After UV aging of 200KWh, comparing with a colorimeter, selecting an area on the material and circling to mark, measuring initial b value of the material by the colorimeter of Japan Meinenda, and recording as b0(ii) a After aging, the b value of the same area is measured and recorded as b1. Difference of yellowing color Δ b ═ b1-b0。
Sixth comprehensive evaluation
"good" means acceptable performance, "excellent" means excellent performance, "Δ" means general performance, and "x" means poor performance.
The specific test results are shown in table 3:
TABLE 3
From the above test data, it can be seen that the back sheets prepared from the adhesives of examples 1 to 9 have a peel force from the substrate of 5.5 to 6.5N/cm, a thermal shock resistance of 200 times or more (no bubble, delamination, cracking, fluorine film shrinkage and yellowing), a resistance to wet heat aging of 2000 hours or more (no bubble, delamination, cracking, fluorine film shrinkage and yellowing), a yellowing index Δ b of 1.5 to 2.0 after 200KWh UV aging, and a visible light transmittance of 84% or more. The epoxy modified polyester adhesive has excellent adhesive force to a base material film, hydrolysis resistance, low yellowing index after ultraviolet aging resistance and wide processing window, and the solar backboard using the adhesive can keep long-term reliable double-sided power generation efficiency when applied to a double-sided battery assembly.
The applicant states that the epoxy modified polyester adhesive, the solar photovoltaic back sheet and the solar photovoltaic cell module containing the same, and the preparation method and application thereof are illustrated by the above examples, but the invention is not limited to the above examples, i.e. the invention is not meant to be implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (22)
1. An epoxy modified polyester adhesive with a crosslinking degree of more than 95 percent is characterized by comprising the following raw materials in parts by weight: 90-110 parts of epoxy modified polyester resin, 8-20 parts of isocyanate curing agent, 0.1-5 parts of ultraviolet absorbent and 1-3 parts of carbodiimide type hydrolysis-resistant auxiliary agent:
the epoxy modified polyester resin comprises the following raw materials in parts by weight: 90-110 parts of polyester resin and 2-20 parts of hydrogenated epoxy resin;
the preparation raw materials of the polyester resin comprise dibasic acid, dihydric alcohol and a catalyst with the molar mass ratio of (1-1.2) to (1) (0.01-0.05);
the dibasic acid is a mixture of aromatic dibasic acid and aliphatic dibasic acid; the molar percentage of the aromatic dibasic acid is below 70 mol% based on the total molar mass of the dibasic acid as 100 mol%;
the dihydric alcohol is C3-C20 alkylene glycol or a mixture of C3-C20 alkylene glycol and C1-C2 alkylene glycol, and the molar mass of the C3-C20 alkylene glycol is more than 50 mol% based on the total molar mass of the dihydric alcohol being 100 mol%;
the hydrogenated epoxy resin is hydrogenated aliphatic epoxy resin;
the preparation method of the epoxy modified polyester resin specifically comprises the following steps:
(1) preparation of polyester resin: mixing and stirring dibasic acid, dihydric alcohol and a catalyst at the temperature of 160 ℃ and 240 ℃ for 3-5h, and heating and reacting at the temperature of 260 ℃ and 270 ℃ under the pressure of less than or equal to 50Pa for 2-4h to obtain the polyester resin;
(2) epoxy modified polyester resin: adding hydrogenated epoxy resin into the polyester resin obtained in the step (1), mixing and stirring for 2-5h at 230-240 ℃, and reacting to obtain the epoxy modified polyester resin with the crosslinking degree of more than 95%;
the acid value of the epoxy modified polyester resin is below 1mg KOH/g;
the carbodiimide type hydrolysis-resistant additive is polycarbodiimide.
2. The epoxy modified polyester binder of claim 1 wherein the aromatic diacid comprises any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, or trimellitic anhydride.
3. The epoxy modified polyester adhesive of claim 1, wherein the aliphatic dibasic acid comprises any one of adipic acid, sebacic acid, or 1, 4-cyclohexanedicarboxylic acid, or a combination of at least two thereof.
4. The epoxy modified polyester adhesive of claim 1, wherein the C3-C20 alkylene glycol comprises any one of 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-methyl-2-ethyl-1, 3-propanediol, or 1, 4-cyclohexanedimethanol, or a combination of at least two thereof.
5. The epoxy modified polyester adhesive of claim 1, wherein the C1-C2 alkylene glycol is ethylene glycol.
6. The epoxy modified polyester adhesive of claim 1, wherein the catalyst is antimony trioxide.
7. The epoxy-modified polyester adhesive according to claim 1, wherein the step (1) is carried out in a stainless steel reaction vessel equipped with a stirrer, a cooling tube and a thermometer.
8. The epoxy-modified polyester adhesive according to claim 1, wherein step (1) is performed under nitrogen protection.
9. The epoxy modified polyester adhesive according to claim 1, wherein the epoxy modified polyester resin has an intrinsic viscosity of 0.3 to 0.8 dl/g.
10. The epoxy modified polyester adhesive of claim 1, wherein the isocyanate curing agent is a reactive isocyanate curing agent.
11. The epoxy modified polyester adhesive of claim 10, wherein the reactive isocyanate curing agent comprises any one of hexamethylene diisocyanate, hexamethylene diisocyanate dimer, hexamethylene diisocyanate trimer, isophorone diisocyanate dimer, isophorone diisocyanate trimer, xylylene diisocyanate dimer, or xylylene diisocyanate trimer, or a combination of at least two thereof.
12. The epoxy modified polyester adhesive of claim 11, wherein the reactive isocyanate curing agent is any one of hexamethylene diisocyanate, hexamethylene diisocyanate dimer, or hexamethylene diisocyanate trimer, or a combination of at least two thereof.
13. The epoxy-modified polyester adhesive of claim 1, wherein the uv absorber comprises any one or a combination of at least two of o-hydroxybenzophenones, benzotriazoles, salicylates, triazines, or substituted acrylonitriles.
14. A solar photovoltaic back sheet comprising a fluorocarbon resin layer, a polyester insulating film layer, an adhesive layer and a weather-resistant film layer laminated in this order, wherein the adhesive layer is made of the epoxy-modified polyester adhesive according to any one of claims 1 to 13.
15. The solar photovoltaic backsheet according to claim 14, wherein the fluorocarbon resin layer is prepared from a material comprising any one or a combination of at least two of a copolymer of tetrafluoroethylene/vinyl ether, a copolymer of chlorotrifluoroethylene and vinyl ester, a copolymer of chlorotrifluoroethylene and vinyl ether, or polyvinylidene fluoride.
16. The solar photovoltaic backsheet according to claim 14, wherein said polyester insulating film layer is a polyethylene terephthalate film.
17. The solar photovoltaic backsheet according to claim 14, wherein the weatherable film layer comprises any one of or a combination of at least two of a polyvinyl fluoride film, a polyvinylidene fluoride film, a tetrafluoroethylene and ethylene copolymer film, a polyethylene terephthalate film.
18. The solar photovoltaic backsheet according to claim 14, wherein the fluorocarbon resin layer has a thickness of 1 to 10 μm.
19. The solar photovoltaic back sheet of claim 14, wherein the thickness of the polyester insulating film layer is 200-300 μm.
20. The solar photovoltaic backsheet according to claim 14, wherein the adhesive layer has a thickness of 5-15 μ ι η.
21. The solar photovoltaic backsheet according to claim 14, wherein the weatherable film layer has a thickness of 10-50 μm.
22. A solar photovoltaic cell module comprising the solar photovoltaic backsheet of any one of claims 14-21.
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| CN109762500A (en) * | 2018-12-28 | 2019-05-17 | 苏州赛伍应用技术股份有限公司 | A kind of photovoltaic backboard adhesive and its preparation method and application |
| CN110643316A (en) * | 2019-09-27 | 2020-01-03 | 上海乘鹰新材料有限公司 | Yellowing-resistant adhesive for transparent solar backboard and preparation method thereof |
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| CN109762500A (en) * | 2018-12-28 | 2019-05-17 | 苏州赛伍应用技术股份有限公司 | A kind of photovoltaic backboard adhesive and its preparation method and application |
| CN110643316A (en) * | 2019-09-27 | 2020-01-03 | 上海乘鹰新材料有限公司 | Yellowing-resistant adhesive for transparent solar backboard and preparation method thereof |
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