CN114350298A - Polyurethane adhesive and application thereof - Google Patents
Polyurethane adhesive and application thereof Download PDFInfo
- Publication number
- CN114350298A CN114350298A CN202210038040.XA CN202210038040A CN114350298A CN 114350298 A CN114350298 A CN 114350298A CN 202210038040 A CN202210038040 A CN 202210038040A CN 114350298 A CN114350298 A CN 114350298A
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- Prior art keywords
- acrylate
- methacrylate
- hydroxyl
- polymer
- mass
- Prior art date
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- Granted
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 92
- 239000000853 adhesive Substances 0.000 title claims abstract description 89
- 239000004814 polyurethane Substances 0.000 title claims abstract description 84
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 84
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 112
- 229920000642 polymer Polymers 0.000 claims abstract description 102
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 100
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 35
- 239000004970 Chain extender Substances 0.000 claims abstract description 33
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 37
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 20
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 12
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 12
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 12
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 12
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 12
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 12
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 10
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 6
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 6
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 abstract description 30
- 150000002513 isocyanates Chemical class 0.000 abstract description 30
- 230000032683 aging Effects 0.000 abstract description 8
- 239000012790 adhesive layer Substances 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 230000000704 physical effect Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 15
- 238000007731 hot pressing Methods 0.000 description 15
- 238000005303 weighing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 3
- 238000007719 peel strength test Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane adhesive and application thereof, wherein the polyurethane adhesive comprises the following components: the main agent comprises a hydroxyl component and a chain extender, the hydroxyl component comprises a hydroxyl-containing acrylate polymer and/or a hydroxyl-containing methacrylate polymer, and the curing agent comprises an isocyanate-containing acrylate polymer and/or an isocyanate-containing methacrylate polymer. The polyurethane adhesive can meet the use requirement that the backboard and the EVA film in the solar cell backboard have excellent hot-press bonding strength after hot-press bonding, and the backboard/the EVA film can still keep high-strength bonding after damp-heat resistance and aging.
Description
Technical Field
The invention belongs to the field of production and application of adhesives, and particularly relates to a polyurethane adhesive and application thereof.
Background
The solar cell is used outdoors for at least 25 years. The solar cell module structure containing the back sheet is generally glass/EVA/wafer/EVA/back sheet. In order to ensure the service life of the battery pack, the adhesive and the film used for manufacturing the solar cell back plate are generally required to have sufficient weather resistance, and in order to ensure that the back plate can effectively protect the cell in the actual use process, the back plate and the EVA film are required to have excellent hot-pressing adhesive strength after being subjected to hot pressing, and the back plate/EVA film can still maintain high-strength adhesion after being subjected to wet-heat aging. However, the back sheet made of the conventional adhesive for solar cell back sheets generally has the defects of poor adhesion and insufficient moist heat resistance after the back sheet is thermally pressed with EVA.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a polyurethane adhesive and an application thereof, wherein the polyurethane adhesive can overcome the defects of poor adhesion and insufficient moist heat resistance after the back sheet prepared by the existing adhesive for the solar cell back sheet is hot-pressed with EVA.
In one aspect of the invention, a polyurethane binder is provided. According to an embodiment of the present invention, the polyurethane binder includes: the main agent comprises a hydroxyl component and a chain extender, the hydroxyl component comprises a hydroxyl-containing acrylate polymer and/or a hydroxyl-containing methacrylate polymer, and the curing agent comprises an isocyanate-containing acrylate polymer and/or an isocyanate-containing methacrylate polymer.
The polyurethane adhesive provided by the embodiment of the invention takes the hydroxyl component comprising the hydroxyl-containing acrylate polymer and/or the hydroxyl-containing methacrylate polymer and the chain extender as the main agent, the main chain structure of the acrylate and/or methacrylate polymer contains a carbon-carbon chain segment with good hydrolysis resistance, and the ester group which is easy to generate hydrolysis reaction is positioned at the side chain position, and the crosslinking net structure is obtained after the hydroxyl component and isocyanate are cured, in addition, the side group of the acrylate polymer containing hydroxyl and/or the methacrylate polymer containing hydroxyl and the crosslinking structure formed after isocyanate is cured have larger steric hindrance, which is beneficial to improving the heat resistance and the humidity and heat hydrolysis resistance of the adhesive layer. On the other hand, the polyurethane adhesive takes acrylate polymer containing isocyanate group and/or methacrylate polymer containing isocyanate group as curing agent, compared with trimer formed by aliphatic or aromatic diisocyanate used in the prior art, the isocyanate polymer has higher molecular weight, and can obviously improve the cohesion and heat resistance of the curing system, the cured adhesive layer shows more excellent heat resistance in the high-temperature hot pressing process, and the main chain of the isocyanate polymer is carbon bond, and the side chain is isocyanate-containing part, so the structure has good weather resistance, and is beneficial to improving the whole humidity and heat resistance of the adhesive. In conclusion, the polyurethane adhesive of the present application has excellent adhesion after thermocompression bonding and moist heat resistance, and can be used for bonding a fluororesin film or a polyolefin film to a polyester film, the adhesive layer (polyolefin layer) and EVA of the prepared solar cell back plate have the peel strength of more than or equal to 120N/15mm, the peel strength of more than or equal to 80N/15mm after the back plate/EVA hot-pressed assembly is aged for 50h at 121 ℃ under 100% RH, the back plate/EVA hot-pressed assembly does not generate the back plate adhesive layer shrinkage phenomenon after being aged for 100h at 121 ℃ under 100% RH, the back plate adhesive layer shrinkage phenomenon is not generated after being aged for 3000h at 85 ℃ under 85% RH, therefore, the polyurethane adhesive can meet the use requirement that the backboard and the EVA film in the solar cell backboard have excellent hot-press bonding strength after hot-press bonding, and the backboard/the EVA film can still maintain high-strength bonding after damp-heat resistant aging.
In addition, the polyurethane adhesive according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, the molar ratio of NCO in the curing agent to OH in the hydroxyl component is 0.5 to 1.1. Thereby, sufficient crosslinking of the active functional groups in the main agent and the curing agent can be achieved.
In some embodiments of the present invention, the chain extender is 1 to 5 parts by mass based on 100 parts by mass of the hydroxyl component in the main agent.
In some embodiments of the invention, the curing agent satisfies at least one of the following conditions: the content of isocyanate groups is 5-10 wt%; the glass transition temperature is-40 to 0 ℃; the weight average molecular weight is 40000-100000. Therefore, the use requirements that the backboard and the EVA film in the solar cell backboard have excellent hot-press bonding strength after hot-press bonding, and the backboard/the EVA can still maintain high-strength bonding after the damp-heat resistant aging can be met.
In some embodiments of the present invention, the acrylate polymer having an isocyanate group is prepared by copolymerizing an acrylate monomer having an isocyanate group with at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, and lauryl acrylate.
In some embodiments of the present invention, the isocyanate group-containing methacrylate polymer is formed by copolymerizing at least one monomer selected from the group consisting of an isocyanate group-containing acrylate monomer and an isocyanate group-containing methacrylate monomer with at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isobornyl methacrylate, and lauryl methacrylate, and at least one monomer in the reactants contains a methyl group.
In some embodiments of the invention, the hydroxyl component satisfies at least one of the following conditions: the hydroxyl value is 25-40 mgKOH/g; the glass transition temperature is-20 to 10 ℃; the weight average molecular weight is 100000-200000. Therefore, the use requirements that the backboard and the EVA film in the solar cell backboard have excellent hot-press bonding strength after hot-press bonding, and the backboard/the EVA can still maintain high-strength bonding after the damp-heat resistant aging can be met.
In some embodiments of the present invention, the hydroxyl-containing acrylate polymer is prepared by copolymerizing at least one monomer selected from 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate with at least one monomer selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, and lauryl acrylate;
in some embodiments of the present invention, the hydroxyl group-containing methacrylate polymer is prepared by reacting at least one monomer selected from the group consisting of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate with at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, and mixtures thereof, At least one monomer of n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isobornyl methacrylate and lauryl methacrylate is copolymerized, and at least one monomer in the reactants contains methyl.
In some embodiments of the invention, the chain extender comprises at least one of glycerol, trimethylolpropane, neopentyl glycol and triethylene glycol.
In a second aspect of the invention, a solar cell backsheet is presented. According to an embodiment of the present invention, the solar cell back sheet has the above polyurethane binder. Therefore, the peel strength of the adhesive layer (polyolefin layer) and EVA of the solar cell back plate is more than or equal to 120N/15mm, the peel strength of the back plate/EVA hot-pressed part is more than or equal to 80N/15mm after the back plate/EVA hot-pressed part is aged for 50h at 121 ℃ and 100% RH, the back plate adhesive layer shrinkage phenomenon is not generated after the back plate/EVA hot-pressed part is aged for 100h at 121 ℃ and 100% RH, the back plate adhesive layer shrinkage phenomenon is not generated after the back plate/EVA hot-pressed part is aged for 3000h at 85 ℃ and 85% RH, and therefore the solar cell back plate has high interlayer peel strength and excellent humidity-heat aging resistance.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In a first aspect of the invention, a polyurethane binder is provided. According to an embodiment of the present invention, the polyurethane binder includes: the main agent comprises a hydroxyl component and a chain extender, the hydroxyl component comprises a hydroxyl-containing acrylate polymer and/or a hydroxyl-containing methacrylate polymer, and the curing agent comprises an isocyanate-containing acrylate polymer and/or an isocyanate-containing methacrylate polymer. It is noted that the hydroxyl component as defined herein does not include a chain extender containing hydroxyl groups.
The inventor finds that the polyurethane adhesive takes a hydroxyl component comprising a hydroxyl-containing acrylate polymer and/or a hydroxyl-containing methacrylate polymer and a chain extender as a main agent, the main chain structure of the acrylate and/or methacrylate polymer contains a carbon-carbon chain segment with good hydrolysis resistance, and an ester group which is easy to undergo hydrolysis reaction is positioned at a side chain position, a cross-linked network structure is obtained after the hydroxyl component and isocyanate are cured, the main chain in the structure can keep good stability and avoid the reduction of the bonding strength when the hydroxyl component and the isocyanate are damaged at high temperature and high humidity, and in addition, the side group of the hydroxyl-containing acrylate polymer and/or the hydroxyl-containing methacrylate polymer and the cross-linked structure formed after the isocyanate are cured have larger steric hindrance, thereby being beneficial to improving the heat resistance and the wet-heat hydrolysis resistance of an adhesive layer; on the other hand, the polyurethane adhesive takes acrylate polymer containing isocyanate group and/or methacrylate polymer containing isocyanate group as curing agent, compared with trimer formed by aliphatic or aromatic diisocyanate used in the prior art, the isocyanate polymer has higher molecular weight, and can obviously improve the cohesion and heat resistance of the curing system, the cured adhesive layer shows more excellent heat resistance in the high-temperature hot pressing process, and the main chain of the isocyanate polymer is carbon bond, and the side chain is isocyanate-containing part, so the structure has good weather resistance, and is beneficial to improving the whole humidity and heat resistance of the adhesive. In conclusion, the polyurethane adhesive of the present application has excellent adhesion after thermocompression bonding and moist heat resistance, and can be used for bonding a fluororesin film or a polyolefin film to a polyester film, the adhesive layer (polyolefin layer) and EVA of the prepared solar cell back plate have the peel strength of more than or equal to 120N/15mm, the peel strength of more than or equal to 80N/15mm after the back plate/EVA hot-pressed assembly is aged for 50h at 121 ℃ under 100% RH, the back plate/EVA hot-pressed assembly does not generate the back plate adhesive layer shrinkage phenomenon after being aged for 100h at 121 ℃ under 100% RH, the back plate adhesive layer shrinkage phenomenon is not generated after being aged for 3000h at 85 ℃ under 85% RH, therefore, the polyurethane adhesive can meet the use requirement that the backboard and the EVA film in the solar cell backboard have excellent hot-press bonding strength after hot-press bonding, and the backboard/the EVA film can still maintain high-strength bonding after damp-heat resistant aging.
Further, the molar ratio of NCO in the curing agent to OH in the hydroxyl component is 0.5 to 1.1, and specifically may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1. The inventors have found that, if the molar ratio of NCO in the curing agent to OH in the hydroxyl component is too low, crosslinking of OH of the reactive functional group in the main agent and NCO of the reactive functional group in the curing agent is insufficient, so that the cohesive force of the cured adhesive layer is insufficient and the heat resistance is lowered. Therefore, by adopting the molar ratio range, the full crosslinking of the active functional groups in the main agent and the curing agent can be realized, so that the cured glue layer has excellent cohesive force and heat resistance.
Further, in the above main agent, the chain extender is 1 to 5 parts by mass based on 100 parts by mass of the hydroxyl component. The inventors have found that if the hydroxyl component is added too much, i.e. the chain extender is added too little, the heat resistance of the cured bondline is insufficient; and if the hydroxyl component is added too little, the chain extender is added too much, so that the adhesive force of the adhesive layer is reduced. Therefore, the adhesive layer has excellent heat resistance and adhesive property by adopting the addition amount of the chain extender. It should be noted that the specific type of chain extender can be selected by those skilled in the art according to actual needs, and for example, the chain extender includes at least one of glycerol, trimethylolpropane, neopentyl glycol and triethylene glycol.
Further, the curing agent satisfies at least one of the following conditions: the content of isocyanate groups is 5 to 10 wt%, specifically 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%; the glass transition temperature is-40 to 0 ℃, preferably-25 to-5 ℃; the weight average molecular weight is 40000-100000, preferably 60000-90000. The inventor finds that if the content of the isocyanate group is too high, excessive crosslinking is easily caused to reduce the adhesive force of a glue line; if the content of the isocyanate group is too low, insufficient crosslinking is easily caused, so that the humidity resistance and the heat resistance of the cured adhesive layer are reduced. Meanwhile, if the glass transition temperature is too low, the heat resistance of the cured adhesive layer is easy to be insufficient, and apparent defects appear in the wet heat and hot pressing test process; if the glass transition temperature is too high, the adhesive force of the cured adhesive layer is insufficient, and if the weight average molecular weight is too high, the adhesive has high viscosity and is not easy to construct; if the weight average molecular weight is too low, the heat resistance of the adhesive is lowered, resulting in edge shrinkage or delamination during hot pressing. Therefore, by adopting the curing agent, the adhesive is easy to construct, and the adhesive layer has excellent heat resistance and adhesive property.
The specific type of the acrylate polymer containing an isocyanate group and the methacrylate polymer containing an isocyanate group can be selected by those skilled in the art according to actual needs, for example, the acrylate polymer containing an isocyanate group is obtained by copolymerizing an acrylate monomer containing an isocyanate group with at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, and lauryl acrylate; the methacrylate polymer containing isocyanate group is prepared from at least one of acrylate monomer containing isocyanate group and methacrylate monomer containing isocyanate group, and at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate and lauryl acrylate, at least one monomer of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isobornyl methacrylate and lauryl methacrylate is copolymerized, and at least one monomer in the reactants contains methyl.
Further, the above-mentioned hydroxyl component satisfies at least one of the following conditions: a hydroxyl value of 25 to 40mgKOH/g, preferably 25 to 30 mgKOH/g; the glass transition temperature is-20 to 10 ℃, preferably-10 to 5 ℃; the weight average molecular weight is 100000-200000, preferably 120000-180000. The inventor finds that if the hydroxyl value is too low, the heat resistance of the adhesive layer after curing is poor, and the phenomenon of back plate adhesive layer edge shrinkage or delamination in the peeling process after back plate/EVA hot pressing is easily caused; if the hydroxyl value is too high, excessive crosslinking is easily caused, so that the adhesive force of the adhesive layer is reduced. Meanwhile, if the glass transition temperature is too low, the heat resistance of the cured adhesive layer is reduced, and the defect of apparent edge shrinkage or delamination is easy to occur in a damp-heat test or a lamination test; if the glass transition temperature is too high, the wettability of the polyurethane adhesive to the substrate is poor, and the adhesive force is reduced. In addition, if the weight average molecular weight is too low, the cohesive force of the polymer adhesive layer is low, so that the adhesive force of the adhesive is reduced, and the heat resistance is insufficient; if the weight average molecular weight is too high, the viscosity of the system is too high to be used easily. Therefore, by adopting the hydroxyl component, the adhesive is easy to construct, and the adhesive layer has excellent heat resistance and adhesive property.
It should be noted that the specific type of the hydroxyl group-containing acrylate polymer and the hydroxyl group-containing methacrylate polymer can be selected by those skilled in the art according to actual needs, for example, the hydroxyl group-containing acrylate polymer is obtained by copolymerizing at least one monomer selected from 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate with at least one monomer selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, and lauryl acrylate; the hydroxyl-containing methacrylate polymer is prepared by mixing at least one monomer selected from 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate with at least one monomer selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, n-butyl methacrylate, and n-butyl methacrylate, At least one monomer of n-octyl methacrylate, isooctyl methacrylate, isobornyl methacrylate and lauryl methacrylate, and at least one monomer in the reactants contains methyl.
In a second aspect of the invention, a solar cell backsheet is presented. According to an embodiment of the present invention, the solar cell back sheet has the above polyurethane binder. Therefore, the peel strength of the adhesive layer (polyolefin layer) and EVA of the solar cell back plate is more than or equal to 120N/15mm, the peel strength of the back plate/EVA hot-pressed part is more than or equal to 80N/15mm after the back plate/EVA hot-pressed part is aged for 50h at 121 ℃ and 100% RH, the back plate adhesive layer shrinkage phenomenon is not generated after the back plate/EVA hot-pressed part is aged for 100h at 121 ℃ and 100% RH, the back plate adhesive layer shrinkage phenomenon is not generated after the back plate/EVA hot-pressed part is aged for 3000h at 85 ℃ and 85% RH, and therefore the solar cell back plate has high interlayer peel strength and excellent humidity-heat aging resistance. It should be noted that the features and advantages described above for the polyurethane adhesive are also applicable to the solar cell back sheet, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Preparation of the hydroxyl component:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, continuously dropwise adding 19 parts by mass of n-butyl acrylate, 32 parts by mass of methyl methacrylate, 23 parts by mass of cyclohexyl methacrylate, 6 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of isooctyl acrylate and 0.6 part by mass of azobisisobutyronitrile after uniformly mixing into the reaction system within 2 hours, keeping the temperature for 3 hours, and then cooling to room temperature to obtain a hydroxyl-containing methacrylate polymer A1 solution, wherein the content of the hydroxyl-containing methacrylate polymer is 50 wt%, and the related physical property parameters of the hydroxyl-containing methacrylate polymer A1 are shown in Table 1.
Preparation of the curing agent:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, and adding 10 parts by mass of methyl methacrylate, 44.5 parts by mass of n-butyl acrylate and 26.5 parts by mass of n-butyl methacrylate19 parts by mass of isocyanate ethyl methacrylate and 1 part by mass of azobisisobutyronitrile are continuously dripped into the reaction system within 2 hours after being uniformly mixed, the temperature is kept for 3 hours and then is reduced to room temperature, so that the methacrylate polymer B4 solution containing isocyanate groups is obtained, the content of the methacrylate polymer B4 containing isocyanate groups is 50 wt%, and the related physical property parameters of the methacrylate polymer B4 containing isocyanate groups are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A1 solution, 53.4 parts by mass of an isocyanate-containing methacrylate polymer B4 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 2
Preparation of the hydroxyl component:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, uniformly mixing 32 parts by mass of n-butyl acrylate, 26.5 parts by mass of methyl methacrylate, 20 parts by mass of cyclohexyl methacrylate, 6.5 parts by mass of 2-hydroxyethyl methacrylate, 15 parts by mass of isooctyl acrylate and 0.3 part by mass of azobisisobutyronitrile, continuously dropwise adding into the reaction system within 2 hours, keeping the temperature for 3 hours, and cooling to room temperature to obtain a hydroxyl-containing methacrylate polymer A4 solution, wherein the content of the hydroxyl-containing methacrylate polymer A4 is 50 wt%, and the related physical property parameters of the hydroxyl-containing methacrylate polymer A4 are shown in Table 1.
Preparation of the curing agent As in example 1
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A4 solution, 23 parts by mass of an isocyanate-containing methacrylate polymer B4 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain a polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 3
Preparation of the hydroxyl component:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, continuously dropwise adding 58 parts by mass of n-butyl acrylate, 32.8 parts by mass of cyclohexyl methacrylate, 9.2 parts by mass of 2-hydroxyethyl methacrylate and 0.4 part by mass of azobisisobutyronitrile into the reaction system within 2 hours after uniformly mixing, keeping the temperature for 3 hours, and then cooling to room temperature to obtain a hydroxyl-containing methacrylate polymer A3 solution, wherein the content of the hydroxyl-containing methacrylate polymer A3 is 50 wt%, and related physical property parameters of the hydroxyl-containing methacrylate polymer A3 are shown in Table 1.
Preparation of the curing agent:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, 41.5 parts by mass of n-butyl acrylate, 6.5 parts by mass of n-butyl methacrylate, 30 parts by mass of isooctyl acrylate, 22 parts by mass of isocyanate ethyl methacrylate and 1 part by mass of azobisisobutyronitrile, uniformly mixing, continuously dropwise adding into a reaction system within 2 hours, keeping the temperature for 3 hours, and cooling to room temperature to obtain a methacrylate polymer B2 solution containing isocyanate groups, wherein the content of the methacrylate polymer B2 containing the isocyanate groups is 50 wt%, and the related physical property parameters of the methacrylate polymer B2 containing the isocyanate groups are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A3 solution, 35.6 parts by mass of an isocyanate-containing methacrylate polymer B2 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 4
Preparation of the hydroxyl component:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, continuously dropwise adding 42 parts by mass of n-butyl acrylate, 40 parts by mass of methyl methacrylate, 8 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of isooctyl acrylate and 0.4 part by mass of azobisisobutyronitrile into a reaction system within 2 hours after uniformly mixing, keeping the temperature for 3 hours, and then cooling to room temperature to obtain a hydroxyl-containing methacrylate polymer A2 solution, wherein the content of the hydroxyl-containing methacrylate polymer A2 is 50 wt%, and related physical property parameters of the hydroxyl-containing methacrylate polymer A2 are shown in Table 1.
Preparation of the curing agent:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2Adding 100 parts by mass of ethyl acetate into an environmental reaction kettle, heating to 75 ℃, uniformly mixing 16.5 parts by mass of methyl methacrylate, 32 parts by mass of n-butyl acrylate, 6.5 parts by mass of n-butyl methacrylate, 15 parts by mass of isooctyl acrylate, 30 parts by mass of isocyanate ethyl methacrylate and 0.7 part by mass of azobisisobutyronitrile, continuously dropwise adding into the reaction system within 2 hours, keeping the temperature for 3 hours, and then cooling to room temperature to obtain a methacrylate polymer B1 solution containing isocyanate groups, wherein the content of the methacrylate polymer B1 containing the isocyanate groups is 50 wt%, and related physical property parameters of the methacrylate polymer B1 containing the isocyanate groups are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A2 solution, 22.6 parts by mass of an isocyanate-containing methacrylate polymer B1 solution and 2 parts by mass of a triethylene glycol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 5
Preparation of the hydroxy component as in example 3
Preparation of the curing agent:
in a device equipped with a mechanical stirrer, a thermometer, a reflux condenser and N2In an environmental reaction kettle, 100 parts by mass of acetic acid is added according to the parts by massHeating ethyl ester to 75 ℃, uniformly mixing 5 parts by mass of methyl methacrylate, 36.5 parts by mass of n-butyl acrylate, 33.5 parts by mass of n-butyl methacrylate, 25 parts by mass of isocyanatoethyl methacrylate and 0.7 part by mass of azobisisobutyronitrile, continuously dropwise adding the mixture into a reaction system within 2 hours, keeping the temperature for 3 hours, and then cooling to room temperature to obtain a methacrylate polymer B3 solution containing isocyanate groups, wherein the content of the methacrylate polymer B3 containing isocyanate groups is 50 wt%, and the related physical property parameters of the methacrylate polymer B3 containing isocyanate groups are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of the prepared hydroxyl-containing methacrylate polymer A3 solution, 31 parts by mass of isocyanate-containing methacrylate polymer B3 solution and 2 parts by mass of triethylene glycol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 6
Preparation of the hydroxy component As in example 1
Preparation of the curing agent As in example 3
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A1 solution, 17.5 parts by mass of an isocyanate-containing methacrylate polymer B2 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 7
The preparation procedure of the hydroxyl component was the same as in example 1, and the specific charge amounts are shown in Table 1: a hydroxyl group-containing acrylic polymer A5 solution was prepared, the content of the hydroxyl group-containing acrylic polymer A5 was 50 wt%, and the parameters of the physical properties of the hydroxyl group-containing acrylic polymer A5 are shown in Table 1.
The procedure for preparing the curing agent is the same as in example 1, and the specific charge amounts are shown in Table 2: the solution of the isocyanate group-containing acrylic polymer B5 was obtained, the content of the isocyanate group-containing acrylic polymer B5 was 50% by weight, and the physical property parameters of the isocyanate group-containing acrylic polymer B5 are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of hydroxyl-containing acrylic polymer A5 solution, 22 parts by mass of isocyanate-containing acrylic polymer B5 solution and 2 parts by mass of glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 8
The preparation procedure of the hydroxyl component was the same as in example 1, and the specific charge amounts are shown in Table 1: the hydroxyl-containing methacrylate polymer A6 solution was prepared, the content of the hydroxyl-containing methacrylate polymer A6 was 50 wt%, and the parameters of the relevant physical properties of the hydroxyl-containing methacrylate polymer A6 are shown in Table 1.
The procedure for preparing the curing agent is the same as in example 1, and the specific charge amounts are shown in Table 2: the isocyanate group-containing methacrylate polymer B6 solution was obtained, the content of the isocyanate group-containing methacrylate polymer B6 was 50 wt%, and the physical property parameters of the isocyanate group-containing methacrylate polymer B6 are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A6 solution, 22 parts by mass of an isocyanate-containing methacrylate polymer B6 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 9
The preparation procedure of the hydroxyl component was the same as in example 1, and the specific charge amounts are shown in Table 1: the hydroxyl-containing methacrylate polymer A7 solution was prepared, the content of the hydroxyl-containing methacrylate polymer A7 was 50 wt%, and the parameters of the relevant physical properties of the hydroxyl-containing methacrylate polymer A7 are shown in Table 1.
The procedure for preparing the curing agent is the same as in example 1, and the specific charge amounts are shown in Table 2: the isocyanate group-containing methacrylate polymer B7 solution was obtained, the content of the isocyanate group-containing methacrylate polymer B7 was 50 wt%, and the physical property parameters of the isocyanate group-containing methacrylate polymer B7 are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A7 solution, 27.5 parts by mass of an isocyanate-containing methacrylate polymer B7 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 10
The preparation procedure of the hydroxyl component was the same as in example 1, and the specific charge amounts are shown in Table 1: the hydroxyl-containing methacrylate polymer A8 solution was prepared, the content of the hydroxyl-containing methacrylate polymer A8 was 50 wt%, and the parameters of the relevant physical properties of the hydroxyl-containing methacrylate polymer A8 are shown in Table 1.
The procedure for preparing the curing agent is the same as in example 1, and the specific charge amounts are shown in Table 2: the solution of the isocyanate group-containing acrylic polymer B8 was obtained, the content of the isocyanate group-containing acrylic polymer B8 was 50% by weight, and the physical property parameters of the isocyanate group-containing acrylic polymer B8 are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A8 solution, 30 parts by mass of an isocyanate-containing acrylate polymer B8 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Example 11
The preparation procedure of the hydroxyl component was the same as in example 1, and the specific charge amounts are shown in Table 1: the hydroxyl-containing methacrylate polymer A9 solution was prepared, the content of the hydroxyl-containing methacrylate polymer A9 was 50 wt%, and the parameters of the relevant physical properties of the hydroxyl-containing methacrylate polymer A9 are shown in Table 1.
The procedure for preparing the curing agent is the same as in example 1, and the specific charge amounts are shown in Table 2: the isocyanate group-containing methacrylate polymer B9 solution was obtained, the content of the isocyanate group-containing methacrylate polymer B9 was 50 wt%, and the physical property parameters of the isocyanate group-containing methacrylate polymer B9 are shown in Table 2.
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A9 solution, 30 parts by mass of an isocyanate-containing methacrylate polymer B9 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 3.
Comparative example 1
Preparation of the hydroxy component As in example 1
Preparing a polyurethane adhesive:
100 parts by mass of a hydroxyl-containing methacrylate polymer A1 solution, 2.23 parts by mass of N3300(HDI type polyisocyanate, manufacturer: Kostew) and 2 parts by mass of a glycerol chain extender are weighed and mixed uniformly to obtain a polyurethane adhesive, and the performance characterization of the polyurethane adhesive is shown in Table 4.
Comparative example 2
Preparation of the hydroxy component As in example 1
Preparing a polyurethane adhesive:
100 parts by mass of a hydroxyl-containing methacrylate polymer A1 solution, 4.4 parts by mass of N3300(HDI type polyisocyanate, manufacturer: Kostew) and 2 parts by mass of a glycerol chain extender are weighed and mixed uniformly to obtain a polyurethane adhesive, and the performance characterization of the polyurethane adhesive is shown in Table 4.
Comparative example 3
Preparation of the hydroxyl component and curing agent As in example 4
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A2 solution, 3.2 parts by mass of an isocyanate-containing methacrylate polymer B1 solution and 2 parts by mass of a glycerol chain extender, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 4.
Comparative example 4
Preparation of the hydroxyl component and curing agent As in example 4
Preparing a polyurethane adhesive:
weighing 100 parts by mass of a hydroxyl-containing methacrylate polymer A2 solution and 22.6 parts by mass of an isocyanate-containing methacrylate polymer B1 solution, mixing uniformly to obtain the polyurethane adhesive, wherein the performance characterization of the polyurethane adhesive is shown in Table 4.
Table 1 shows the charge amounts of the hydroxyl group-containing methacrylate polymers A1 to A9 and the physical property parameters related to the products.
TABLE 1
Table 2 shows the amounts of isocyanate group-containing methacrylate polymers B1 to B9 and the physical property parameters of the products.
TABLE 2
The sample performance evaluation method comprises the following steps:
1. preparation of solar cell back sheet
The used base materials of PET film, polyolefin film and fluorine film are all subjected to corona treatment. Coating the prepared polyurethane adhesive solution on a PET film, wherein the dry adhesive is 5-10 g/m2Respectively and fully attaching the fluorine film and the polyolefin film to the PET layer at a certain temperature and under a certain pressure, and curing for 48 hours at 45-55 ℃ to obtain the solar cell backboard.
2. Preparation of backboard/EVA hot-pressing assembly
1) Cutting the back plate into back plate sample strips of 30cm multiplied by 1.5 cm;
2) taking a piece of transparent toughened glass with the size of 20cm multiplied by 20cm, sequentially stacking the EVA film and the backboard sample strip in the step 1) above the glass, enabling the bonding layer of the backboard sample strip to be in direct contact with the EVA, standing for 20 minutes at the temperature of 130-150 ℃ and the vacuum degree of-0.95-0.9 MPa, taking out and cooling to obtain the backboard/EVA hot-pressed part.
3. Performance test of initial back plate/EVA hot-pressing assembly
3.1 initial appearance
Observing the appearance of the back plate/EVA hot-pressing assembly, recording the appearance of the bonding layer,
the back plate bonding layer has no shrinkage and no hole, and is marked as O; the test can be continued as 3.2;
the back plate bonding layer has a shrinkage phenomenon or a hole phenomenon, and is marked as x; no 3.2 tests were performed.
3.2 initial Peel Strength
Referring to the method in the national standard GB/T2790-1995 'adhesive 180 DEG peel strength test method for flexible material to rigid material', the back plate sample strip in the back plate/EVA hot-pressing assembly is peeled off at the peeling speed of 100mm/min, the numerical average value in the peeling process of the back plate and the EVA is recorded,
the peel strength of the back plate/EVA is more than or equal to 150N/15mm, and the mark is O;
the peel strength of the back plate/EVA is less than or equal to 120N/15mm and less than 150N/15mm, and the mark is delta;
the peel strength of the back sheet/EVA was < 120N/15mm, marked x;
4. moisture and heat resistance test of back plate/EVA hot-pressing part
4.1PCT 50 hr Performance
The back plate/EVA hot-pressed part is placed for 50 hours at the temperature of 121 ℃ and in the environment of 100 percent RH, then is placed for 1 day at the room temperature, and is subjected to the peel strength test according to the method of the sample performance evaluation method item 3,
1) apparent appearance
The back plate adhesive layer and the PET film are not layered and marked as O;
the back plate bonding layer and the PET film are layered, marked as x, and no peel strength test is performed;
2) peel strength
The peel strength of the back plate/EVA is more than or equal to 120N/15mm, and the mark is O;
the peel strength of the back plate/EVA is less than or equal to 80N/15mm and less than 120N/15mm, and the mark is delta;
the peel strength of the back plate/EVA is less than 80N/15mm, and marked as x;
4.2PCT 100 hours appearance
The appearance of the back plate bonding layer is observed after the back plate/EVA hot-pressing assembly is placed for 100 hours at the temperature of 121 ℃ and the RH of 100 percent,
the back plate bonding layer has no shrinkage and no hole, and is marked as O;
the back plate bonding layer has a shrinkage phenomenon or a hole phenomenon, and is marked as x;
4.3 "double 85" appearance
The back plate/EVA hot-pressing assembly is taken out after being placed for 3000 hours in the environment of 85 ℃ and 85 percent RH, the appearance of the back plate bonding layer is observed,
the back plate bonding layer has no shrinkage and no hole and is marked as O;
the shrinkage or hole phenomenon of the back plate bonding layer is marked as x.
Table 3 shows the charge amount of the polyurethane binder and the related physical parameters and properties of the product in examples 1-11.
TABLE 3
Table 4 shows the charge amount of the polyurethane binder and the relevant physical parameters and properties of the product in comparative examples 1-4.
TABLE 4
As can be seen from the data in tables 3 and 4, the polyurethane binders prepared in comparative examples 1 and 2, in which at least one of an acrylate polymer containing an isocyanate group and a methacrylate polymer containing an isocyanate group was not added as a curing agent and N3300 was added as a curing agent, resulted in insufficient initial peel strength or wet heat resistance of the hot-pressed parts. In addition, NCO in comparative example 3: OH is out of the scope of this application and represents an undesirable initial appearance of the hot pressed part. Therefore, the polyurethane adhesive prepared by mixing the hydroxyl component, the chain extender and the curing agent according to a certain proportion can be used for obtaining a back plate/EVA hot-pressing assembly with excellent performance. Comparative example 4 does not contain a chain extender, and the appearance is normal in the hot press bonding process, but the adhesive strength is insufficient after the damp-heat test, and the apparent shrinkage phenomenon is easy to occur.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A polyurethane adhesive, comprising: the main agent comprises a hydroxyl component and a chain extender, wherein the hydroxyl component comprises a hydroxyl-containing acrylate polymer and/or a hydroxyl-containing methacrylate polymer,
the curing agent comprises an acrylate polymer containing isocyanate groups and/or a methacrylate polymer containing isocyanate groups.
2. The polyurethane binder of claim 1, wherein the molar ratio of NCO in the curing agent to OH in the hydroxyl component is 0.5 to 1.1.
3. The polyurethane binder according to claim 1, wherein the chain extender is 1 to 5 parts by mass based on 100 parts by mass of the hydroxyl component in the main agent.
4. The polyurethane binder of any one of claims 1-3, wherein the curing agent satisfies at least one of the following conditions:
the content of isocyanate groups is 5-10 wt%;
the glass transition temperature is-40 to 0 ℃;
the weight average molecular weight is 40000-100000.
5. The polyurethane binder according to claim 4, wherein the acrylate polymer having the isocyanate group is obtained by copolymerizing an acrylate monomer having the isocyanate group with at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate and lauryl acrylate;
optionally, the methacrylate polymer containing isocyanate group is prepared by mixing at least one selected from acrylate monomer containing isocyanate group and methacrylate monomer containing isocyanate group with at least one selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, lauryl acrylate, at least one monomer of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isobornyl methacrylate and lauryl methacrylate is copolymerized, and at least one monomer in the reactants contains methyl.
6. The polyurethane binder of any one of claims 1-3, wherein the hydroxyl component satisfies at least one of the following conditions:
the hydroxyl value is 25-40 mgKOH/g;
the glass transition temperature is-20 to 10 ℃;
the weight average molecular weight is 100000-200000.
7. The polyurethane binder of claim 6, wherein the hydroxyl-containing acrylate polymer is prepared by copolymerizing at least one monomer selected from the group consisting of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate with at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, and lauryl acrylate;
optionally, the hydroxyl-containing methacrylate polymer is prepared by mixing at least one monomer selected from 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate with at least one monomer selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, isobornyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, n-butyl methacrylate, and n-butyl methacrylate, At least one monomer of cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isobornyl methacrylate and lauryl methacrylate is copolymerized, and at least one monomer in reactants contains methyl.
8. The polyurethane binder of any one of claims 1-3, wherein the chain extender comprises at least one of glycerol, trimethylolpropane, neopentyl glycol, and triethylene glycol.
9. A solar cell back sheet comprising the polyurethane adhesive according to any one of claims 1 to 8.
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| CN115799507A (en) * | 2022-07-29 | 2023-03-14 | 浙江碳一新能源有限责任公司 | Natural graphite negative electrode material with surface connected with binder, and preparation method and application thereof |
| CN116948128A (en) * | 2023-09-20 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Graft polymer, preparation method, positive electrode plate, secondary battery and electricity utilization device |
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| CN116948128B (en) * | 2023-09-20 | 2024-02-23 | 宁德时代新能源科技股份有限公司 | Graft polymer, preparation method, positive electrode plate, secondary battery and electricity utilization device |
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