CN116200161A - Adhesive for solvent-free solar cell backboard and preparation method thereof - Google Patents

Adhesive for solvent-free solar cell backboard and preparation method thereof Download PDF

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CN116200161A
CN116200161A CN202211674899.6A CN202211674899A CN116200161A CN 116200161 A CN116200161 A CN 116200161A CN 202211674899 A CN202211674899 A CN 202211674899A CN 116200161 A CN116200161 A CN 116200161A
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adhesive
solar cell
solvent
agent
polyol
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鲍建楠
滕赟
冯斯旸
付洪娥
王新
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Shenyang Research Institute of Chemical Industry Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
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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
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to an adhesive suitable for PO/PET and PVDF/PET of a solar cell backboard, in particular to an adhesive for a solvent-free solar cell backboard and a preparation method thereof. The polyurethane prepolymer comprises two components of a main agent and a curing agent, wherein the main agent is copolymerized polyester polyol, and the curing agent is isocyanate-terminated polyurethane prepolymer generated by the reaction of the polyol and isocyanate; wherein the mass ratio of isocyanate groups in the curing agent to hydroxyl groups in the main agent is 1.2-1.8:1. the solar cell backboard prepared by using the adhesive has higher peel strength between PO/PET and PVDF/PET layers after normal state and PCT aging for 96 hours, almost has no yellowing, and can completely meet the application performance requirements of the adhesive for the solar cell backboard.

Description

Adhesive for solvent-free solar cell backboard and preparation method thereof
Technical Field
The invention relates to an adhesive suitable for PO/PET and PVDF/PET of a solar cell backboard, in particular to an adhesive for a solvent-free solar cell backboard and a preparation method thereof.
Background
The solar cell backboard is an important component of the photovoltaic power generation equipment and mainly plays roles of electric insulation, moisture blocking and cell sheet protection and is positioned on the back of the solar cell board. The solar cell back plates under the current production process are divided into a composite type and a coating type. The composite type material is formed by compounding multiple layers of materials with different functions together by using an adhesive, wherein the outer protective layer generally provides excellent weather resistance by using PVDF, the base film provides certain strength by using PET, and the inner layer plays a certain buffering role by using PO or EVA; the coating is to coat a layer of fluorocarbon coating on the surface of the substrate, and provide weather resistance by using the fluorine-containing coating.
At present, adhesives used for bonding materials of all layers of the solar cell backboard are solvent adhesives. Solvent-based adhesives have the risk of fire or explosion during storage and use, and volatilization of solvents can cause harm to the bodies of users and pollute the environment. In addition, the solvent type adhesive needs to be dried and compounded after being coated, the process of drying the solvent needs a certain time to severely limit the production efficiency, and the subsequent recovery or treatment of the solvent also needs the cost.
The solvent-free adhesive has better safety in the storage and use processes because the solvent-free adhesive does not contain solvent, and the drying and solvent recovery are not needed, so that the production line speed is obviously improved, and the composite cost is reduced. Along with the enhancement of environmental awareness of domestic enterprises and the limitation of national policies, the solvent-free adhesive provides a new bonding solution.
Disclosure of Invention
The invention aims to provide an adhesive for a solvent-free solar cell backboard, which can improve the moisture and heat resistance of the adhesive for the solvent-free solar cell backboard, enable the adhesive to resist PCT (Pressure Cooker Test) aging for 96 hours or double 85 aging for 3000 hours, and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the adhesive for the solvent-free solar cell backboard consists of two components, namely a main agent and a curing agent, wherein the main agent is a polyester polyol containing copolymerization, and the curing agent is an isocyanate-terminated polyurethane prepolymer generated by the reaction of the polyol and isocyanate; wherein the mass ratio of isocyanate groups in the curing agent to hydroxyl groups in the main agent is 1.2-1.8:1.
when the mass ratio of the isocyanate groups to the hydroxyl groups is too large, the residual isocyanate groups can continuously react with moisture to generate carbon dioxide gas to influence the water resistance and high temperature resistance of the adhesive, and when the mass ratio of the isocyanate groups to the hydroxyl groups is too small, the adhesive is incompletely cured to influence the adhesive property, and the interlayer peeling strength is small.
The polyol is copolymerized polyester polyol with the water content below 400ppm and polyether polyol; wherein, the molecular weight of the copolymerized polyester polyol used in the main agent and the curing agent is 500-4000, the structural unit contains an aliphatic cyclic structure, preferably 700-2500, and the structural unit contains an aliphatic cyclic structure; the polyether polyol used in the curing agent has a molecular weight of 500 to 4000, preferably 700 to 2500. If the polyol molecules are too small, the required curing time is longer, and the mechanical properties after curing are poorer; too high a molecular weight of the polyol can result in too high a viscosity of the finished adhesive for application.
The copolymerization type polyester polyol is prepared by mixing a polyacid monomer and a polyol monomer, slowly heating to 220-230 ℃, filling nitrogen for protection, carrying out esterification reaction, and discharging water, wherein the end of the esterification reaction is judged when the water discharge reaches the theoretical water discharge; continuously heating to 230-240 deg.c, maintaining vacuum degree-0.09-0.1 MPa for 2-4 hr to obtain the copolymer polyester polyol with water content below 400 ppm.
The alkyd ratio is 1.2-1.6:1.
The polyester polyol was measured for acid value and hydroxyl value, and the molecular weight of the polyester polyol was calculated using the following formula.
Figure BDA0004016817130000021
Wherein the measurement of the amount of the hydroxyl group is performed in accordance with the measurement of the hydroxyl group value in the HG/T2709-95 polyester polyol, and the measurement of the acid group is performed in accordance with the measurement of the acid group value in the HG/T2708-95 polyester polyol. If the polyester polyol monomers are dibasic acid and dihydric alcohol, the functionality of the polyester polyol is 2.
The polybasic acid monomer is selected from one or more of 1, 2-cyclohexane dicarboxylic acid, 1, 2-cyclohexane dicarboxylic anhydride (hexahydrophthalic anhydride), 1, 3-cyclohexane dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, 1, 6-adipic acid, 1, 9-azelaic acid and 1, 10-sebacic acid; wherein the aliphatic polybasic acid structural unit is required to reach more than 20wt%, preferably more than 30wt% of the total mass of the polyester polyol, so that the polyester polyol can show more excellent high temperature resistance and hydrolysis resistance, and can keep good adhesion capability under high temperature and high humidity.
The polyol monomer is selected from one or more of 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol (neopentyl glycol) and trimethylolpropane.
The main agent is a main agent component obtained by heating one or more copolymerized polyester polyols with the water content below 400ppm to 60-80 ℃, adding an auxiliary agent under the protection of nitrogen, and uniformly mixing.
Wherein, the moisture content is measured by a Karl Fischer type moisture meter, and if the measured value is more than 400ppm, the polyol needs to be dehydrated and pretreated. The pretreatment method is to add the copolymerized polyester polyol into a reaction vessel, raise the temperature to 100-120 ℃ and keep the vacuum degree between-0.09 and-0.1 MPa. The moisture content was measured at intervals until the moisture content was below 400 ppm.
The auxiliary agent is an antioxidant, an anti-hydrolysis agent, a light stabilizer and a silane coupling agent, wherein the antioxidant, the anti-hydrolysis agent, the light stabilizer and the silane coupling agent respectively account for 0.02-0.5wt%, 0.1-2wt% and 0.02-0.5wt% of the mass of the copolymerized polyester polyol.
The antioxidant mainly comprises a hindered phenol antioxidant, and the action mechanism is to prevent the subsequent free radical chain reaction by capturing free radicals generated during the decomposition of organic matters, so that the occurrence of organic matter molecular degradation and yellowing is effectively saved. In the invention, the addition of the antioxidant can improve the heat oxidation resistance and photo oxidation resistance of the adhesive. Can be selected from BASF commercial products IRGANOX 1010, IRGANOX 1076, IRGANOX 1098, IRGANOX 245, IRGANOX 1330, IRGANOX 3114, and can be used together with other types of antioxidants, such as IRGAFOS 168, IRGAFOS 38, IRGAFOS 126, IRGANOX PS 802, etc.
The hydrolysis inhibitor mainly comprises carbodiimide hydrolysis inhibitor which mainly acts with carboxyl generated by hydrolysis to generate crosslinking and inhibit the hydrolysis promotion effect of the carboxyl. Optionally one or more of Stabaxol 1LF, stabaxol MTC, stabaxol P200, casbexilate V-02B, casbexilate V-05, hyMax 220, hyMax 1010, all of which are commercially available from RheinChemie, and all of which are commercially available from Nisshinbo.
The main effects of the light stabilizer include the conversion of harmful ultraviolet rays and the capture of free radicals activated by illumination. Can be selected from one or more of BASF commercial products Chimassorb 81, chimassorb 944, chimassorb2020, tinuvin 326, tinuvin 328, tinuvin 329, tinuvin 234, tinuvin 360, tinuvin 1577FF, tinuvin 1600, uvinol 4050 FF.
The silane coupling agent includes, but is not limited to, one or more of vinyltris (beta-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, gamma- (meth) acryloxypropyl trimethoxysilane, gamma- (meth) acryloxypropyl triethoxysilane, gamma- (meth) acryloxypropyl dimethoxymethylsilane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) methyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl triethoxysilane, beta- (3, 4-epoxycyclohexyl) methyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyldiethoxysilane, gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, N-phenyl-gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane.
The curing agent is prepared by adding one or more polyether polyols or copolymerized polyester polyols with the water content below 400ppm into a reaction vessel, heating to 60-80 ℃, adding isocyanate under the protection of nitrogen, heating to 80-100 ℃, maintaining for 0.5-4 h, adding a catalyst, and continuing to react until the isocyanate group content in the system is not reduced any more, thus obtaining a curing agent component; wherein the mass ratio of the polyol to the isocyanate is 0.5-2:1, the catalyst is 0.02-0.1 wt% of the total mass of the raw materials (polyol and isocyanate).
Too little isocyanate is added, the viscosity of the curing agent component is too high, and the application process of the product is affected; when the addition amount of isocyanate is too large, the molecular weight of the curing agent component is smaller, the curing time required in practical application is longer, and the mechanical property after curing is poorer.
Wherein the amount of isocyanate group substances is determined according to the determination mode of the content of isocyanate groups in the GB/T29493.6-2013 polyurethane prepolymer.
The polyether polyol used by the curing agent is one or more selected from polyethylene glycol, polytetrahydrofuran glycol and hydroxyl-terminated polybutadiene.
The isocyanate in the curing agent component is one or more selected from isophorone diisocyanate, isophorone diisocyanate trimer, hexamethylene diisocyanate trimer and hydrogenated diphenylmethane diisocyanate.
The catalyst in the curing agent component is selected from one or more of tin octoate, dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurate and tin chloride.
The preparation method of the adhesive for the solvent-free solar cell backboard comprises the steps of mixing the main agent and the curing agent; wherein the mass ratio of isocyanate groups in the curing agent to hydroxyl groups in the main agent is 1.2-1.8:1.
use of the solvent-free adhesive for a solar cell back sheet, the solvent-free adhesive being suitable for a solar cell back sheet that is resistant to PCT accelerated aging (121 ℃, saturated humidity) for 96 hours. The invention has the advantages that:
the adhesive consists of two parts, namely a main agent and a curing agent. Wherein the curing agent mainly comprises an isocyanate-terminated copolymerized polyester polyol and polyether polyol mixture; the main agent mainly comprises copolymerized polyester polyol and auxiliary agent.
In general, the main structure of the adhesive has more polyester components, the monomer containing the alicyclic structure is adopted in the synthesis of the copolymerized polyester, and the rest of the components contain more side chains, so that the purpose of protecting ester groups and reducing hydrolysis rate is achieved while the rigidity of the main structure of the adhesive is enhanced. The adhesive has high peel strength between PO/PET and PVDF/PET layers after being used for the solar cell backboard, normal state and PCT aging for 96 hours, almost has no yellowing, and can completely meet the application performance requirements of the adhesive for the high-performance solar backboard.
Detailed Description
The invention is further described by the following detailed description. It should be noted that the following examples should not be taken as a basis for limiting the scope of the present invention, but merely for facilitating understanding of the technical scheme of the present invention.
Example 1
Preparation of the copolyol P-1: 745.62g of 1, 2-cyclohexanedicarboxylic acid, 111.69g of 1, 6-adipic acid and 352.56g of 2, 2-dimethyl-1, 3-propanediol (neopentyl glycol) are added into a reaction vessel, nitrogen is replaced for three times, the mixture is slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 235 ℃, the vacuum degree is kept for 30kPa to react for 2.5 hours, and the copolymerized polyester polyol P-1 is prepared, and the number average molecular weight is 825.
Example 2
Preparation of the copolyol P-2: 745.62g of 1, 2-cyclohexanedicarboxylic acid, 143.82g of 1, 9-azelaic acid and 352.56g of 2, 2-dimethyl-1, 3-propanediol (neopentyl glycol) are added into a reaction vessel, nitrogen is replaced for three times, the mixture is slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 235 ℃, the vacuum degree is kept for 30kPa to react for 2.5 hours, and the copolymerized polyester polyol P-2 with the number average molecular weight of 997 is prepared.
Example 3
Preparation of the copolyol P-3: 745.62g of 1, 2-cyclohexanedicarboxylic acid, 154.53g of 1, 10-sebacic acid and 352.56g of 2, 2-dimethyl-1, 3-propanediol (neopentyl glycol) are added into a reaction vessel, nitrogen is replaced for three times, the mixture is slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 235 ℃, the vacuum degree is kept for 30kPa to react for 2.5 hours, and the copolymerized polyester polyol P-3 with the number average molecular weight 1031 is prepared.
Example 4
Preparation of the copolyol P-4: 745.62g of 1, 2-cyclohexanedicarboxylic acid, 143.82g of 1, 9-azelaic acid, 282.05g of 2, 2-dimethyl-1, 3-propanediol (neopentyl glycol) and 98.99g of 3-methyl-1, 5-pentanediol are added into a reaction vessel, nitrogen is replaced for three times, the mixture is mixed and slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 235 ℃, the vacuum degree is kept for 30kPa to react for 2.5 hours, and the copolymerized polyester polyol P-4 with the number average molecular weight of 876 is prepared.
Example 5
Preparation of the copolyol P-5: 372.81g of 1, 2-cyclohexanedicarboxylic acid, 372.81g of 1, 4-cyclohexanedicarboxylic acid, 143.82g of 1, 9-azelaic acid, 282.05g of 2, 2-dimethyl-1, 3-propanediol (neopentyl glycol) and 98.99g of 3-methyl-1, 5-pentanediol are added into a reaction vessel, nitrogen is replaced for three times, the mixture is mixed and slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 240 ℃, the vacuum degree is kept for 30kPa for 3 hours, and the copolymerized polyester polyol P-5 and the number average molecular weight 1105 are prepared.
Example 6
Preparation of the copolyol P-6: 372.30g of 1, 6-adipic acid, 479.4g of 1, 9-azelaic acid and 61.02g of 1, 4-cyclohexanedimethanol 390.53,2-methyl-1, 3-propanediol are added into a reaction vessel, nitrogen is replaced for three times, the mixture is slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 240 ℃, the vacuum degree is kept for 30kPa for 3 hours, and the copolymerized polyester polyol P-6 is prepared, and the number average molecular weight is 1004.
Example 7
Preparation of the copolyol P-7: 372.30g of 1, 6-adipic acid, 479.4g of 1, 9-azelaic acid and 113.88g of 1, 4-cyclohexanediol 235.94,3-methyl-1, 5-pentanediol are added into a reaction vessel, nitrogen is replaced for three times, the mixture is slowly heated to 220 ℃, after the esterification reaction is finished, the temperature in the reaction vessel is continuously heated to 240 ℃, the vacuum degree is kept for 30kPa for 3 hours, and the copolymerized polyester polyol P-7 is prepared, and the number average molecular weight 967.
Example 8
Preparation of a solvent-free adhesive main agent A-1: adding 240g of copolymerized polyester polyol P-1, 3g of silane coupling agent gamma-glycidoxypropyl trimethoxy silane, 1010.05 g of antioxidant IRGANOX, 2g of hydrolysis inhibitor carbodilite eV-02B and 2020.1 g of light stabilizer Chimassorb into a reaction vessel, heating to 90 ℃ to melt raw materials, and stirring to 120rpm to uniformly mix the raw materials to obtain the solvent-free adhesive main agent A-1.
The solvent-free adhesive main agent A-2 to A-7 in the preparation process of the embodiment can be obtained by replacing the copolymerized polyester polyol P-1 with the different copolymerized polyester polyols (P-2 to P-7) in the corresponding preparation of the embodiment 2-6 according to the description, wherein the copolymerized polyester polyol P-2 is added into the solvent-free adhesive main agent A-2, and the like.
Example 9
Preparation of curing agent S-1: adding copolymerization type polyester polyol P-1 300g and polypropylene glycol 510g (molecular weight 1000) into a reaction kettle container, heating to 70-80 ℃ to melt raw materials, starting stirring to 120rpm to uniformly mix the raw materials, adding isophorone diisocyanate 697g, slowly heating the reaction kettle to 90 ℃, reacting at constant temperature for 1h, adding catalyst dibutyltin dilaurate 0.75g, and then maintaining the reaction temperature at 95 ℃ for reacting for 1h to obtain a curing agent S-1. The isocyanate group content of curing agent S-1 was found to be 9.27%.
Example 10
Preparation of curing agent S-2: adding copolymerization type polyester polyol P-1 300g and polypropylene glycol 510g (molecular weight 1000) into a reaction kettle container, heating to 70-80 ℃ to melt raw materials, starting stirring to 120rpm to uniformly mix the raw materials, adding isophorone diisocyanate 697g, slowly heating the reaction kettle to 90 ℃, reacting at constant temperature for 1h, adding catalyst dibutyltin dilaurate 0.75g, maintaining the reaction temperature at 95 ℃ for reacting for 1h, and adding hexamethylene diisocyanate trimer 75g to obtain the curing agent S-2. The isocyanate group content of curing agent S-2 was measured to be 10.26%.
The following table describes the preheating of the different main agents and the different curing agents to 60℃respectively, according to the isocyanate group content in the curing agent and the hydroxyl group content in the main agent of 1.4:1, and is evenly mixed and coated on PET base material. The laminator was preheated to 60℃and the PVDF film and PO film were each laminated with PET using a pressure of 0.6MPa, and cured at 60℃for 144 hours. The thickness of the adhesive film after curing was measured to be in the range of 5 to 10. Mu.m.
Peel strength test: according to the 180 DEG peel strength test method of GB-T2790-1995 adhesive, a flexible material is measured on a rigid material standard, a composite film sample is cut into a strip shape of 15mm multiplied by 200mm, the unbonded ends of the materials on two sides of a tested adhesive layer are respectively and symmetrically clamped on an upper clamp and a lower clamp of a universal tester, the clamping part is ensured not to slide, namely the applied tensile force is uniformly distributed on the width of the sample, the tester is started, the upper clamp and the lower clamp are separated at the speed of 100mm/min, and the interlayer peel strength of the corresponding material is given by the tester.
Since the bulk strength of PVDF films is low, peel strength cannot be measured effectively. The adhesion properties of PVDF/PET were determined as described in GB/T1720-79 (89) paint film adhesion assay.
PCT accelerated aging test: the composite film was placed in a PCT accelerated aging test chamber, the inside of the chamber was kept in communication with the outside, the temperature was raised to 100 ℃ at a rate of 10 ℃/min, the exhaust valve was closed, and the temperature was continued to be raised to 121 ℃, at which time the absolute pressure in the chamber was about 2.3atm. And (3) starting timing when the temperature reaches 121 ℃, keeping the temperature at 121+/-0.5 ℃ and under the condition of 2.3+/-0.1 atm for 48h/96h, taking out the composite film, standing for 24h until the water is completely volatilized, and testing the interlayer peeling strength by the peeling strength testing method.
The test data are shown in the following table:
Figure BDA0004016817130000071
from the interlayer peeling strength test results in the table, the solvent-free bi-component solar cell backboard adhesive prepared by the invention has good bonding performance on PO/PET and PVDF/PET, the normal interlayer peeling strength is more than or equal to 9N/cm, and the interlayer peeling strength is more than or equal to 4N/cm after PCT accelerated aging for 96 hours, and the adhesive has good bonding performance, so that the hydrolysis resistance and the wet heat resistance of the adhesive can meet the requirements of a high-performance solar cell backboard.
Testing yellowing resistance: the yellow edge index Δb of the back plate was measured for PCT aged samples according to the specifications of GB/T3979-2008 and GB/T7921-2008. The color difference value of all the samples is less than 2, and almost no obvious yellowing exists, so that the product has good yellowing resistance.
The foregoing is only a part of the preferred embodiments of the present invention, and the scope of the claims of the present invention is not limited thereto. Variations or substitutions that would be obvious to one of ordinary skill in the art in light of the present disclosure are intended to be included within the scope of the present invention, which is defined by the following claims.

Claims (9)

1. The adhesive for the solvent-free solar cell backboard is characterized by comprising two components of a main agent and a curing agent, wherein the main agent is copolymerized polyester polyol, and the curing agent is isocyanate-terminated polyurethane prepolymer generated by the reaction of the polyol and isocyanate; wherein the mass ratio of isocyanate groups in the curing agent to hydroxyl groups in the main agent is 1.2-1.8:1.
2. the adhesive for a solvent-free solar cell back sheet according to claim 1, wherein: the polyol is copolymerized polyester polyol with the water content below 400ppm and polyether polyol; wherein, the molecular weight of the copolymerized polyester polyol used in the main agent and the curing agent is 500-4000, and the structural unit contains an aliphatic cyclic structure; the polyether polyol used in the curing agent has a molecular weight of 500 to 4000.
3. The adhesive for a solvent-free solar cell back sheet according to claim 1 or 2, characterized in that: the copolymerization type polyester polyol is prepared by mixing a polyacid monomer and a polyol monomer, slowly heating to 220-230 ℃, filling nitrogen for protection, carrying out esterification reaction, and discharging water, wherein the end of the esterification reaction is judged when the water discharge reaches the theoretical water discharge; continuously heating to 230-240 deg.c, maintaining vacuum degree-0.09-0.1 MPa for 2-4 hr to obtain the copolymer polyester polyol with water content below 400 ppm.
4. The adhesive for a solvent-free solar cell back sheet according to claim 3, wherein: the polybasic acid monomer is selected from one or more of 1, 2-cyclohexane dicarboxylic acid, 1, 2-cyclohexane dicarboxylic anhydride (hexahydrophthalic anhydride), 1, 3-cyclohexane dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, 1, 6-adipic acid, 1, 9-azelaic acid and 1, 10-sebacic acid;
the polyol monomer is selected from one or more of 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol (neopentyl glycol) and trimethylolpropane.
5. The adhesive for a solvent-free solar cell back sheet according to claim 1, wherein: the main agent is a main agent component obtained by heating one or more copolymerized polyester polyols with the water content below 400ppm to 60-80 ℃, adding an auxiliary agent under the protection of nitrogen, and uniformly mixing.
6. The adhesive for a solvent-free solar cell back sheet according to claim 5, wherein: the auxiliary agent is an antioxidant, an anti-hydrolysis agent, a light stabilizer and a silane coupling agent, wherein the antioxidant, the anti-hydrolysis agent, the light stabilizer and the silane coupling agent respectively account for 0.02-0.5wt%, 0.1-2wt% and 0.02-0.5wt% of the mass of the copolymerized polyester polyol.
7. The adhesive for a solvent-free solar cell back sheet according to claim 1, wherein: the curing agent is prepared by adding one or more polyether polyols or copolymerized polyester polyols with the water content below 400ppm into a reaction vessel, heating to 60-80 ℃, adding isocyanate under the protection of nitrogen, heating to 80-100 ℃, maintaining for 0.5-4 h, adding a catalyst, and continuing to react until the isocyanate group content in the system is not reduced any more, thus obtaining a curing agent component; wherein the mass ratio of the polyol to the isocyanate is 0.5-2:1, the catalyst is 0.02-0.1 wt% of the total mass of the raw materials (polyol and isocyanate).
8. A method for preparing the adhesive for the solvent-free solar cell backboard according to claim 1, which is characterized in that: mixing the main agent and the curing agent; wherein the mass ratio of isocyanate groups in the curing agent to hydroxyl groups in the main agent is 1.2-1.8:1.
9. use of the adhesive for a solvent-free solar cell back sheet according to claim 1, characterized in that: the solvent-free adhesive is suitable for a solar cell back sheet which can resist PCT accelerated aging (121 ℃ C., saturated humidity) for 96 hours.
CN202211674899.6A 2022-12-26 2022-12-26 Adhesive for solvent-free solar cell backboard and preparation method thereof Pending CN116200161A (en)

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CN118480168A (en) * 2024-07-15 2024-08-13 山东尚正新材料科技股份有限公司 High-weather-resistance photovoltaic backboard adhesive and preparation method thereof

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