CN108546539B - Weather-resistant two-component polyurethane adhesive and solar cell back plate - Google Patents

Weather-resistant two-component polyurethane adhesive and solar cell back plate Download PDF

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CN108546539B
CN108546539B CN201810331935.6A CN201810331935A CN108546539B CN 108546539 B CN108546539 B CN 108546539B CN 201810331935 A CN201810331935 A CN 201810331935A CN 108546539 B CN108546539 B CN 108546539B
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hydroxyl
weight
polyol
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adhesive
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CN108546539A (en
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李永杰
田丛
黄建滔
刘瀛
姜伟
赵伟建
陈月霞
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China Lucky Group Corp
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China Lucky Group Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • 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
    • 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

Abstract

The invention discloses a weather-resistant two-component polyurethane adhesive, the main agent of the adhesive consists of a hydroxyl-terminated polyurethane prepolymer A and a polyacrylate polyol B, the hydroxyl-terminated polyurethane prepolymer A is obtained by polymerizing polyester polyol and difunctional isocyanate, and a curing agent is a multifunctional isocyanate compound. The hydroxyl-terminated polyurethane prepolymer A accounts for 50-70 parts by weight of the main agent, the polyacrylate polyol B accounts for 30-50 parts by weight of the main agent, and the equivalent ratio NCO/OH of hydroxyl in the main agent to isocyanate group in the curing agent is 0.5-2.0. The adhesive of the invention can realize high adhesion between the base film layers and can still maintain good adhesion strength after high-temperature high-humidity aging test.

Description

Weather-resistant two-component polyurethane adhesive and solar cell back plate
Technical Field
The invention relates to a weather-resistant two-component polyurethane adhesive which still has excellent bonding effect after being exposed and aged under long-term damp and hot conditions, and the technology can be applied to solar cell back plates or other outdoor industrial fields.
Background
Solar energy is the cleanest, safe and reliable energy source in the future. The photovoltaic industry is becoming an increasingly explosive industry following the IT and microelectronic industries internationally. The solar cell is used outdoors for at least 25 years, and therefore, the multilayer thin film that can be used for the solar cell back sheet needs to have sufficient weather resistance. The adhesive used for compounding the structural layers has comprehensive performance advantages of good application property, high bonding strength, high heat resistance, ultraviolet aging resistance, long-term moisture and thermal hydrolysis resistance and the like to meet the use requirements of the field.
The patent CN102643622A relates to a solvent-based two-component polyurethane adhesive, wherein the component A is polyhydroxy unsaturated resin, the glass transition temperature is 20-50 ℃, the component B is-NCO end-capped prepolymer obtained by the addition reaction of polyol and diisocyanate, the polyurethane adhesive obtained by the method has good weather resistance, but the adhesive with high glass transition temperature can reduce the wettability of a film to a certain degree, so that the initial adhesion of the composite is reduced, and the interlayer displacement is easy to occur in the process of compounding and rolling.
Other patents mainly based on prepolymers, such as CN105524588A, disclose a solvent-free composite adhesive for solar cell back sheets, the technology has no solvent volatilization, can improve the peeling strength between the adhesive and the base material, can keep the peeling force between PET/PVDF layers at 4.5N/1.5cm after a double 85 test for 2000h, and in order to ensure that the adhesive finally keeps good coating viscosity, in the technology, polyether polyol and isocyanate are reacted to obtain a terminal-NCO prepolymer, and the terminal-NCO prepolymer, the polyether polyol, micromolecule diol and hydrolysis resistant agent form an adhesive formula, because the molecular chain of the polyether polyol is softer and has lower polarity compared with the molecular chain of the polyester polyol and the acrylic polyol, therefore, the strength of the adhesive layer is reduced after the adhesive is cured, and the peeling strength of the system is reduced to a certain extent due to the increase of the content of polyether polyol in the formula composition.
After intensive research on the above problems, the applicant of the present invention found that an adhesive formulation using a polyacrylate polyol having excellent moisture and heat resistance in a prepolymer combination obtained by reacting a polyester polyol and a polycaprolactone polyol with a diisocyanate compound as a main agent and a polyisocyanate polymer as a curing agent has excellent initial peel strength, can realize high adhesion between base film layers after curing, and can maintain good adhesion strength after high-temperature high-humidity aging test, thereby improving the yield of back sheet production and having advantages of cost reduction and energy saving.
Disclosure of Invention
The invention aims to provide a weather-resistant two-component polyurethane adhesive to overcome the defects of poor initial adhesion, insufficient heat resistance and poor wet-heat hydrolysis resistance of the conventional adhesive for a solar back panel.
The technical scheme for solving the technical problem is as follows:
a weather-resistant two-component polyurethane adhesive comprises a main agent and a curing agent, wherein the main agent comprises 50-70 parts by weight of hydroxyl-terminated polyurethane prepolymer A and 30-50 parts by weight of polyacrylate polyol B, the curing agent is polyfunctional isocyanate, the hydroxyl-terminated polyurethane prepolymer A is obtained by polymerizing polyester polyol and difunctional isocyanate, and the polyester polyol further comprises 50-80 parts by weight of polycaprolactone polyol; the proportion of the difunctional isocyanate is 5-10 parts by weight.
In the weather-resistant two-component polyurethane adhesive, the polyacrylate polyol B is obtained by polymerizing a (meth) acrylate monomer having not less than 4 carbon atoms in the structure, wherein the proportion of the (meth) acrylate monomer having a hydroxyl group is 1 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the polyacrylate polyol B.
In the weather-resistant two-component polyurethane adhesive, the Mw of the polycaprolactone polyol is 500-2500, and the hydroxyl value is 45-140 mgKOH/g; the difunctional isocyanate compound is at least one selected from isophorone diisocyanate, diphenylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate.
The glass transition temperature of the polyacrylate polyol B is 0-20 ℃, preferably 5-15 ℃.
In the weather-resistant two-component polyurethane adhesive, the Mw of the polyacrylate polyol B is 20000-100000.
The curing agent is multifunctional isocyanate, and can be selected from one or more mixtures of toluene diisocyanate tripolymer, diphenylmethane diisocyanate tripolymer, isophorone diisocyanate tripolymer and hexamethylene diisocyanate tripolymer.
In the weather-resistant two-component polyurethane adhesive, the equivalent ratio NCO/OH of hydroxyl in a main agent consisting of the hydroxyl-terminated polyurethane prepolymer A and the polyacrylate polyol B to isocyanate in a curing agent is 0.5-2.0.
The adhesive is used for the solar cell back plate and has the following structure:
a solar cell back sheet is composed of more than one film selected from polyester film, fluororesin film and polyolefin film, wherein the weather-resistant two-component polyurethane adhesive is used for compounding the films, and then the films are cured for 2-4 days at 40-50 ℃.
Advantageous effects
The weather-resistant two-component polyurethane adhesive provided by the invention is prepared by using a mixture of a hydroxyl-terminated polyurethane prepolymer A and a polyacrylate polyol B as a main agent and matching multifunctional isocyanate as a curing agent. Has excellent substrate adaptability, and can be used for film compounding of more than one of polyester film, fluororesin film and polyolefin film; after curing, a highly cross-linked network structure with a urethane bond can be formed, so that the adhesive can provide excellent curing peel strength of the composite film, the peel strength of the film product after curing for 2-4 days at 40-50 ℃ is more than or equal to 8.0N/15mm, and the risk of delamination of the back film of the solar cell can be effectively reduced;
as ester bonds are easy to generate hydrolysis reaction in a long-term damp and hot environment, so that the effective bonding performance of the adhesive is reduced, the adhesive designed in the invention uses polyacrylate polyol and hydroxyl-terminated polyurethane prepolymer A as main agent formulas, wherein the main chain of the polyacrylate polyol is of a long carbon chain structure, and the hydroxyl-terminated polyurethane prepolymer also contains polycaprolactone polyol with low ester bond content in the main chain segment, so that an adhesive film formed by curing the adhesive obtained in the invention can enable a composite film product to have long-term effective damp and hot environment adaptability, and the peel strength can be still kept to be more than 6N/15mm after HAST50 hours and bis '85' 2000 hours.
Detailed Description
The main agent of the invention consists of 50-70 parts by weight of hydroxyl-terminated polyurethane prepolymer A and 30-50 parts by weight of polyacrylate polyol B, and the curing agent is polyfunctional isocyanate. The hydroxyl-terminated polyurethane prepolymer A is obtained by polymerizing polyester polyol and difunctional isocyanate, wherein the polyester polyol further comprises 50-80 parts by weight of polycaprolactone polyol; the proportion of the difunctional isocyanate is 5-10 parts by weight.
The polyester polyol can be obtained by polymerizing aromatic or aliphatic carboxylic acid and aliphatic polyol, wherein the aromatic or aliphatic carboxylic acid can be one or a mixture of more of phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid and sebacic acid; the aliphatic polyol can be selected from one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol, neopentyl glycol and trimethylolpropane, in order to improve the weather resistance of the adhesive, the polyester polyol further comprises polycaprolactone polyol, and the polycaprolactone polyol can be formed by initiating epsilon-caprolactone ring-opening polymerization through one or more of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and trimethylolpropane. The polycaprolactone polyol has Mw of 500-2500, hydroxyl value of 45-140mgKOH/g, preferably Mw of 1000-2000, and hydroxyl value of 56-110 mgKOH/g.
The difunctional isocyanate compound used for preparing the hydroxyl-terminated polyurethane prepolymer A can be one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The polyacrylate polyol B is obtained by polymerizing a (meth) acrylate monomer having not less than 4 carbon atoms in the structure, and the proportion of the (meth) acrylate monomer having a hydroxyl group is 1 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the polyacrylate polyol B.
Wherein the (meth) acrylate monomer having not less than 4 carbon atoms may be selected from one or more monomers of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate. In the present invention, at least two of methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate are preferable, and methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, glycidyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, hexyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, isobutyl methacrylate, glycidyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate.
The (meth) acrylate monomer having a hydroxyl group may be a mixture of one or more monomers 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.
The glass transition temperature (Tg) of the polyacrylate polyol B is 0-20 ℃, and preferably 5-15 ℃; mw is 20000-100000, preferably 40000-80000.
When the hydroxyl-terminated polyurethane prepolymer A is contained in an amount of 50 to 70 parts by weight and the polyacrylate polyol B is contained in an amount of 30 to 50 parts by weight based on 100 parts by weight of the base polymer, the adhesive system can exhibit excellent moisture and heat resistance while maintaining good adhesion to the interface of the film, and can realize good adhesive strength even after long-term outdoor exposure.
The curing agent is polyfunctional isocyanate, and can be selected from a mixture based on one or more of toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, isophorone diisocyanate trimer and hexamethylene diisocyanate trimer, preferably one or a mixture of isophorone diisocyanate trimer and hexamethylene diisocyanate trimer.
The equivalent ratio NCO/OH of hydroxyl group contained in the main agent composed of the hydroxyl-terminated polyurethane prepolymer A and the polyacrylate polyol B to isocyanate group in the curing agent is 0.5 to 2.0, preferably 1.0 to 1.5.
In order to more specifically illustrate the technical solution of the present invention, the following further description is provided by way of examples, but the examples are only illustrative and do not limit the scope of the present invention.
Examples
The synthesis method of the hydroxyl-terminated polyurethane prepolymer A1 is as follows:
weighing 40 parts by weight of Dynacoll 7250 and 50 parts by weight of PD1-10 according to the feeding amount in the table 1, adding the Dynacoll 7250 and the PD1-10 into a reaction kettle provided with a mechanical stirrer, a thermometer, a reflux condenser and nitrogen protection, adding 100 parts by weight of ethyl acetate, heating to 75 ℃, after all raw materials are dissolved, dropwise adding 10 parts by weight of Wannate-MDI50 into the reaction system within 1 hour, keeping the temperature for 2 hours, completely reacting, cooling to room temperature, and discharging to obtain a resin solution (with the solid content of 50 wt%) of the hydroxyl-terminated polyurethane prepolymer A1.
The resin solutions of hydroxyl-terminated polyurethane prepolymers A2-A4 were prepared by the same synthetic method as hydroxyl-terminated polyurethane prepolymer A1 according to the weight parts of the materials in Table 1, and the charging amounts of the hydroxyl-terminated polyurethane prepolymers A1-A4 are shown in Table 1.
TABLE 1
Figure BDA0001628222200000051
The details of the ingredients in table 1 are as follows:
dynacoll 7250 (trade name): polyester polyol manufactured by industrial winning group, wherein Mw is 5500, and hydroxyl value is 18-24 mgKOH/g;
dynacoll 7320 (trade name): the Mw of the polyester polyol manufactured by the industrial group is 3500, and the hydroxyl value is 27-34 mgKOH/g;
PD1-10 (trade name): polycaprolactone polyols manufactured by basf corporation, Mw 1000, hydroxyl value 108-;
PD1-20 (trade name): polycaprolactone polyols manufactured by basf corporation, Mw 2000, hydroxyl number 53-59 mgKOH/g;
220EC (trade name): polycaprolactone polyol manufactured by Daiiluo corporation, Mw 2000, hydroxyl number 56mgKOH/g
Wannate-MDI 50: diisocyanate compounds produced by petitchen warfarin chemistry.
The synthesis method of the polyacrylate polyol B1 is as follows:
adding 100 parts by weight of ethyl acetate into a reaction kettle provided with a mechanical stirring device, a thermometer and a reflux condenser pipe, heating to 75 ℃, continuously dropwise adding 33 parts by weight of methyl methacrylate, 50 parts by weight of n-butyl acrylate, 14 parts by weight of cyclohexyl methacrylate, 3 parts by weight of hydroxyethyl methacrylate and 1.1 part by weight of azobisisobutyronitrile into the reaction system within 5 hours after uniformly mixing, preserving the temperature for 3 hours, and then cooling to room temperature to obtain a resin solution of polyacrylate polyol B1 with the weight molecular weight of 41000, the hydroxyl value of 13mgKOH/g and the glass transition temperature of 2 ℃, wherein the solid content is 50 wt%.
The resin solutions of the polyacrylate polyols B2-B4 were prepared by the same synthetic method as the polyacrylate polyol B1 according to the weight parts of the materials in Table 2, and the feeding amounts and the product-related physical property parameters of the polyacrylate polyols B1-B4 are shown in Table 2.
TABLE 2
Figure BDA0001628222200000061
Preparation of the base agent in the examples:
69 parts by weight of a resin solution (50% by weight) of the hydroxyl-terminated polyurethane prepolymer A1 and 31 parts by weight of a resin solution (50% by weight) of the polyacrylate polyol B1 were thoroughly mixed in parts by weight of the components in Table 3 to obtain a main agent 1. The bases 2 to 6 were obtained in the same manner as in the preparation of the base 1.
TABLE 3
Figure BDA0001628222200000062
Figure BDA0001628222200000071
Examples 1 to 6
The adhesive formulations used in examples 1-6 were prepared in the parts by weight indicated in Table 4 and tested using the sample property evaluation method. In Table 4, curing agent C was hexamethylene diisocyanate trimer-type curing agent N3300 (trade name) manufactured by Bayer, NCO content was 21.8% by weight, and solid content was 100%.
The sample performance evaluation method comprises the following steps:
1. preparation of test samples
The used base materials are polyethylene terephthalate film (PET) with the thickness of 125 mu m and 22.5 mu m PVDF film which are respectively processed by corona treatment, the prepared adhesive solution is coated on the PET film, and the coating amount is 20-25g/m2And drying at 80 ℃ for 2 minutes, and fully bonding the PVDF film and the PET film to obtain the composite sample.
2. Initial peel strength test
The peel strength test is carried out by sampling immediately after the preparation of the composite sample wafer, and the test is carried out under the conditions of the peel speed of 300mm/min and the sample width of 15mm by referring to the method in national standard GB/T2790-.
3. Test for peel Strength after aging
The peel strength test of the composite sample piece after curing at 50 ℃ for 48 hours is carried out under the conditions of the peel speed of 300mm/min and the strip width of 15mm by referring to the method in national standard GB/T2790-1995 'adhesive 180 DEG peel strength test method flexible material to rigid material'.
4. HAST aging resistance test
1) HAST50 hour peel strength: the peel strength test of the cured sample piece after being placed for 50 hours at 121 ℃ and 100% humidity is carried out under the conditions of 300mm/min of peel speed and 15mm of sample strip width by referring to the method in national standard GB/T2790-.
2) HAST100 hour appearance: the cured sample piece was left at 121 ℃ and 100% humidity for 100 hours, and then the appearance of the sample was observed, and whether or not the adhesive portion had defects such as shrinkage, bubbling, delamination, etc.
5. Long-term high temperature and high humidity resistance test
The aged specimens were evaluated under the conditions of 85 ℃ and 85% humidity according to the national standard GB/T2423.3-2006, and the standing time of the specimens was 2000 hours.
TABLE 4
Figure BDA0001628222200000081
Comparative examples 1 to 3
Adhesive formulations for comparative examples 1 to 3 were prepared in the weight part formulations of the respective components in table 5, and tested using the same sample property evaluation methods as in the examples.
TABLE 5
Figure BDA0001628222200000082
Figure BDA0001628222200000091
As can be seen from the data in tables 3 and 4, the two-component polyurethane adhesive has excellent initial peel strength, cured peel strength, and wet heat resistance because the two-component polyurethane adhesive contains both hydroxyl-terminated polyurethane prepolymer a and polyacrylate polyol B, and thus the two-component polyurethane adhesive provided in the examples has good adhesion even after the two-component polyurethane adhesive is tested under the harsh condition of two 85 for 2000 hours.
As shown by the results of comparative examples 1 to 3 in Table 5, the formulations of comparative examples 1 and 2 do not contain both the hydroxyl terminated polyurethane prepolymer A and the polyacrylate polyol B, and thus the initial peel strength is low and the excellent aging peel strength or aging resistance cannot be obtained. While the main agent and curing agent ratio of comparative example 3 is out of the claimed range, the initial peel strength, the cured peel strength and the wet heat resistance are inferior to those of the examples.
The two-component polyurethane adhesive provided by the invention can be used for bonding more than one film of polyester film, fluorine resin film and polyolefin film, the obtained composite product not only has excellent initial peel strength, but also has peel strength more than or equal to 8.0N/15mm after the film product is cured at 40-50 ℃ for 2-4 days, and has excellent damp and heat resistance, and the peel strength can still be maintained at more than 6.0N/15mm after HAST50 hours and double '85' 2000 hours.

Claims (3)

1. A weather-resistant two-component polyurethane adhesive comprises a main agent and a curing agent, and is characterized in that: the main agent consists of 50-70 parts by weight of hydroxyl-terminated polyurethane prepolymer A and 30-50 parts by weight of polyacrylate polyol B, the curing agent is polyfunctional isocyanate, the hydroxyl-terminated polyurethane prepolymer A is obtained by polymerizing polyester polyol and difunctional isocyanate, wherein the polyester polyol further comprises 50-80 parts by weight of polycaprolactone polyol; the proportion of the difunctional isocyanate is 5-10 parts by weight;
the polyacrylate polyol B is obtained by polymerizing a (methyl) acrylate monomer with the carbon number not less than 4 in the structure, wherein the proportion of the (methyl) acrylate monomer with hydroxyl is 1-10 parts by weight relative to 100 parts by weight of the polyacrylate polyol B;
the Mw of the polycaprolactone polyol is 500-2500, and the hydroxyl value is 45-140 mgKOH/g; the difunctional isocyanate compound is at least one selected from isophorone diisocyanate, diphenylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate;
the glass transition temperature of the polyacrylate polyol B is 0-20 ℃;
the Mw of the polyacrylate polyol B is 20000-100000;
the equivalent ratio NCO/OH of isocyanate group in the curing agent and hydroxyl group in the main agent consisting of hydroxyl-terminated polyurethane prepolymer A and polyacrylate polyol B is 0.5-2.0.
2. The weatherable, two-component polyurethane adhesive of claim 1, wherein: the curing agent is selected from a mixture based on one or more of toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, isophorone diisocyanate trimer or hexamethylene diisocyanate trimer.
3. A solar cell backsheet, characterized in that: comprising one or more films selected from the group consisting of polyester films, fluororesin films and polyolefin films, wherein the films are obtained by compounding the layers with the weather-resistant two-component polyurethane adhesive according to claim 1 or 2 and then aging the compounded layers at 40 to 50 ℃ for 2 to 4 days.
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