CN113773781A - Double-component solvent-free reaction type polyurethane hot melt adhesive and application thereof - Google Patents

Double-component solvent-free reaction type polyurethane hot melt adhesive and application thereof Download PDF

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Publication number
CN113773781A
CN113773781A CN202111272176.9A CN202111272176A CN113773781A CN 113773781 A CN113773781 A CN 113773781A CN 202111272176 A CN202111272176 A CN 202111272176A CN 113773781 A CN113773781 A CN 113773781A
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component
hot melt
melt adhesive
polyurethane hot
solvent
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王金良
秦瑜
郝旭东
郭永春
刘赣东
徐礼文
李春光
于玉建
周晓楠
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Hubei Jingzhou Huabang Chemical Co ltd
Institute of Chemistry Henan Academy of Sciences Co Ltd
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Hubei Jingzhou Huabang Chemical Co ltd
Institute of Chemistry Henan Academy of Sciences Co Ltd
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Priority to CN202111272176.9A priority Critical patent/CN113773781A/en
Publication of CN113773781A publication Critical patent/CN113773781A/en
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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
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the technical field of polyurethane hot melt adhesives, in particular to a double-component solvent-free reactive polyurethane hot melt adhesive and application thereof. The double-component solvent-free reaction type polyurethane hot melt adhesive comprises a component A and a component B which are independently packaged; the component A comprises a polyurethane prepolymer; the polyurethane prepolymer contains isocyanate; the component B comprises polyester polyol, polycarbonate polyol and an auxiliary agent; the mass ratio of the polyester polyol to the polycarbonate polyol to the auxiliary agent is (70-80): (7-15): (10-17); the mass ratio of the component A to the component B is (10-20): 100. the double-component solvent-free reaction type polyurethane hot melt adhesive has high modulus and strong adhesion in the initial stage of use, is high in curing speed, and is more suitable for the requirements of the solar backboard manufacturing industry on improving the production efficiency and quality control; and meanwhile, after being cured, the resin has more excellent water resistance and chemical resistance and better yellowing resistance.

Description

Double-component solvent-free reaction type polyurethane hot melt adhesive and application thereof
Technical Field
The invention relates to the technical field of polyurethane hot melt adhesives, in particular to a double-component solvent-free reactive polyurethane hot melt adhesive and application thereof.
Background
The adhesive used in the solar backboard industry at present is a two-component solvent type polyurethane adhesive, and the solvent type product has the characteristics of simple use and operation and stable and reliable performance, and is the most widely applied product at present. However, the adhesive contains about 50% of organic solvent, the organic solvent is additionally added to carry out dilution preparation in the using process, about 4g of organic solvent is needed when 1g of dry adhesive is coated, so that the unsafe defects of high environmental pollution, harmlessness to the health of operators, flammability, explosiveness and the like exist, and the problems of high cost, high energy consumption, excessive solvent residue and the like easily occur to a user manufacturer because a large amount of organic solvent is needed to be added for dilution and all the organic solvents are needed to be heated and dried after coating.
The aqueous adhesive is compounded mainly by adopting aqueous acrylate and polyurethane emulsion adhesive, has better initial adhesion, does not need organic solvent to participate in the using process, but has limited performance, no high temperature resistance, no hydrolysis resistance and low strength when being adhered by adopting the adhesive, and cannot meet the requirement of the solar backboard industry on the performance of products at present.
The solvent-free compounding process usually adopts two-component (or single-component) liquid solvent-free polyurethane adhesive, solves the problems of the two compounding modes, and has the advantages of environmental protection, high efficiency, low cost and the like. However, the molecular weight of the bicomponent adhesive is very low, and the bicomponent adhesive is still liquid within a quite long time (0.5-4 h) after being mixed, so that the initial viscosity strength is very poor, and the adhesive can be unevenly shrunk and slightly flows between two layers of films due to the change of temperature and tension after being compounded, so that the serious appearance problems of orange peel and the like are formed. So that the solvent-free polyurethane adhesives in the existing market can not be used for producing solar back plates.
Disclosure of Invention
The invention aims to provide a two-component solvent-free reaction type polyurethane hot melt adhesive and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a double-component solvent-free reaction type polyurethane hot melt adhesive, which comprises a component A and a component B which are independently packaged;
the component A comprises a polyurethane prepolymer; the polyurethane prepolymer contains isocyanate;
the component B comprises polyester polyol, polycarbonate polyol and an auxiliary agent; the mass ratio of the polyester polyol to the polycarbonate polyol to the auxiliary agent is (70-80): (7-15): (10-17);
the mass ratio of the component A to the component B is (10-20): 100, respectively;
the two-component solvent-free reaction type polyurethane hot melt adhesive does not contain a solvent.
Preferably, the functionality of the polyurethane prepolymer is more than or equal to 2, and the mass percentage of the isocyanate in the component A is 10-30%.
Preferably, the preparation raw materials of the polyurethane prepolymer comprise polyisocyanate and a silane coupling agent;
the mass ratio of the polyisocyanate to the silane coupling agent is (97-100): (0-3).
Preferably, the number average molecular weight of the polycarbonate polyol is 500-4000;
the hydroxyl value of the polycarbonate polyol is 28-250 mgKOH/g.
Preferably, the auxiliary agent comprises a catalyst, an anti-hydrolysis agent and a tackifying resin;
the mass ratio of the catalyst to the hydrolysis resistant agent to the tackifying resin is (0.005-2): (0.1-6): (9-14).
Preferably, the catalyst comprises an organic tin catalyst and/or dimorpholinyl diethyl ether;
the hydrolysis resistant agent comprises polycarbodiimide;
the tackifying resin comprises an epoxy resin.
The invention also provides application of the two-component solvent-free reaction type polyurethane hot melt adhesive in the technical scheme in the field of preparation of solar back panels.
Preferably, the method of application comprises the following steps:
respectively melting the component A and the component B and then mixing to obtain a two-component solvent-free reaction type polyurethane hot melt adhesive;
preheating a substrate, coating the surface of the substrate with the two-component solvent-free reactive polyurethane hot melt adhesive, laminating the substrate with another substrate, and curing to obtain the solar backboard.
Preferably, the melting temperature of the component A and the melting temperature of the component B are 80-100 ℃ independently.
Preferably, the curing temperature is 45-60 ℃ and the curing time is 24-48 h.
The invention provides a double-component solvent-free reaction type polyurethane hot melt adhesive, which comprises a component A and a component B which are independently packaged; the component A comprises a polyurethane prepolymer; the polyurethane prepolymer contains isocyanate; the component B comprises polyester polyol, polycarbonate polyol and an auxiliary agent; the mass ratio of the polyester polyol to the polycarbonate polyol to the auxiliary agent is (70-80): (7-15): (10-17); the mass ratio of the component A to the component B is (10-20): 100, respectively; the two-component solvent-free reaction type polyurethane hot melt adhesive does not contain a solvent. The double-component solvent-free reaction type polyurethane hot melt adhesive is a molten liquid at high temperature, so that the coating is convenient, the temperature is reduced after the compounding, and the adhesive is quickly changed into a solid with certain strength, so that the double-component solvent-free reaction type polyurethane hot melt adhesive has higher modulus and stronger adhesion force at the initial stage of use. The component A and the component B of the polyurethane hot melt adhesive can greatly improve the reaction activity of the catalyst at the compounding temperature of 80-100 ℃, so that the curing speed is high after compounding, two film materials with different performances can be quickly positioned, the waiting time is shortened, the appearance condition of a composite product can be quickly checked, and the requirements of the solar backboard manufacturing industry on improving the production efficiency and quality control are met; meanwhile, the cured polyurethane prepolymer has more excellent water resistance and chemical resistance, and the aliphatic isocyanate group contained in the polyurethane prepolymer can make the yellowing resistance of the hot melt adhesive better, so that the hot melt adhesive has wider application prospect.
Detailed Description
The invention provides a double-component solvent-free reaction type polyurethane hot melt adhesive, which comprises a component A and a component B which are independently packaged;
the component A comprises a polyurethane prepolymer; the polyurethane prepolymer contains isocyanate;
the component B comprises polyester polyol, polycarbonate polyol and an auxiliary agent; the mass ratio of the polyester polyol to the polycarbonate polyol to the auxiliary agent is (70-80): (7-15): (10-17);
the mass ratio of the component A to the component B is (10-20): 100, respectively;
the two-component solvent-free reaction type polyurethane hot melt adhesive does not contain a solvent.
In the invention, the mass ratio of the component A to the component B is (10-20): 100, preferably (12-18): 100, more preferably (14 to 16): 100.
in the invention, the component A comprises polyurethane prepolymer; the polyurethane prepolymer comprises isocyanate; the functionality of the polyurethane prepolymer is preferably more than or equal to 2, and more preferably more than or equal to 3; the mass percentage of the isocyanate in the component A is preferably 10-30%, more preferably 15-25%, and most preferably 18-22%.
In the invention, the preparation raw materials of the polyurethane prepolymer preferably comprise polyisocyanate and silane coupling agent; the mass ratio of the polyisocyanate to the silane coupling agent is preferably (97-100): (0-3), more preferably (98-99): (1-2). In the present invention, the polyisocyanate is preferably an HDI trimer; the silane coupling agent is preferably a silane coupling agent containing an epoxy group, and the silane coupling agent containing an epoxy group preferably includes glycidyl ether propyl trimethoxysilane and/or glycidyl ether propyl triethoxysilane. In a specific embodiment of the invention, the HDI trimer is HT100 available from Vanilla-Ciba, and the silane coupling agent is CG-0187 available from caruncle-Dawley chemical Co.
In the invention, the HDI trimer can further increase the hydrolysis resistance, chemical resistance and yellowing resistance of the cured two-component solvent-free reaction type polyurethane hot melt adhesive; the silane coupling agent can further improve the adhesive force between the two-component solvent-free reaction type polyurethane hot melt adhesive and the base material.
In the present invention, the preparation process of the a component preferably includes the steps of:
under the condition of stirring, mixing isocyanate and a silane coupling agent to obtain the component A.
In the present invention, the mixing is preferably performed by adding a silane coupling agent to the isocyanate.
In the invention, the stirring time is preferably 25-35 min; the stirring rate is not particularly limited in the present invention, and may be a rate well known to those skilled in the art.
After the mixing is finished, the invention also preferably comprises filtration, and the filter screen adopted by the filtration is preferably a 400-mesh filter screen.
In the invention, the component B comprises polyester polyol, polycarbonate polyol and an auxiliary agent; the mass ratio of the polyester polyol to the polycarbonate polyol to the auxiliary agent is (70-80): (7-15): (10-17), preferably (72-78): (8-13): (12-16), more preferably (74-76): (10-11): (13-15).
When the amount of the polyester polyol is increased within the above range, the viscosity of the component B is increased, and the viscosity of the component A and the component B after mixing is also increased, so that the initial adhesion, the shear strength and the modulus of the two-component solvent-free reactive polyurethane hot melt adhesive after curing are increased, and the elongation at break is reduced; hydroxyl on the molecular chain of the polyester polyol can be chemically reacted with isocyanic acid radical in the component A to generate urethane group, namely polyurethane. In a specific embodiment of the present invention, the polyester polyol is a H3020 polyester polyol available from great reputation chemical ltd.
In the present invention, the number average molecular weight of the polycarbonate polyol is preferably 500 to 4000, more preferably 500 to 2000, and most preferably 1000 to 1500. The hydroxyl value of the polycarbonate polyol is preferably 28 to 250mgKOH/g, more preferably 50 to 200mgKOH/g, and most preferably 100 to 150 mgKOH/g. In a specific embodiment of the present invention, the polycarbonate polyol is a SYHP1000 polycarbonate polyol available from great reputation chemical ltd.
In the invention, the dosage proportion of the polycarbonate polyol in the range can further improve the hydrolysis resistance of the two-component solvent-free reaction type polyurethane hot melt adhesive after curing and improve the bonding strength after damp-heat aging.
In the present invention, the auxiliary preferably includes a catalyst, an anti-hydrolysis agent and a tackifying resin; the mass ratio of the catalyst to the hydrolysis resistant agent to the tackifying resin is preferably (0.005-2): (0.1-6): (9-14), more preferably (0.01-0.02): (1-3): (10-12).
In the present invention, the catalyst preferably includes an organotin-based catalyst and/or dimorpholinyldiethylether; the organic tin catalyst is preferably dibutyltin dilaurate and/or stannous octoate; when the catalyst is more than two of the above specific choices, the invention has no special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion. In a specific embodiment of the invention, the catalyst is TMG218 (dibutyltin dilaurate) available from Schmidt, Inc.
In the invention, the catalyst can improve the curing speed of the two-component solvent-free reaction type polyurethane hot melt adhesive, improve the initial bonding strength of the two-component solvent-free reaction type polyurethane hot melt adhesive, shorten the curing time and improve the production efficiency.
In the present invention, the hydrolysis resistance agent preferably includes polycarbodiimide. In a specific embodiment of the invention, the hydrolysis resistance agent is an hydrolysis resistance aid P200 (polycarbodiimide) from rhine, germany.
In the invention, the hydrolysis resistance of the two-component solvent-free reaction type polyurethane hot melt adhesive can be improved by the hydrolysis resistant agent, and the bonding strength after damp-heat aging is improved.
In the present invention, the tackifying resin preferably comprises an epoxy resin, more preferably a bisphenol a type epoxy resin; the tackifying resin can improve the modulus and the bonding strength of the cured two-component solvent-free reaction type polyurethane hot melt adhesive and improve the hydrolysis resistance of the cured two-component solvent-free reaction type polyurethane hot melt adhesive. In a specific embodiment of the present invention, the epoxy resin is E-44 epoxy resin available from Yueyanite.
In the present invention, the preparation process of the B component preferably includes the steps of:
and mixing polyester polyol, polycarbonate polyol and an auxiliary agent to obtain the component B.
In the present invention, the mixing is preferably performed by premixing the polyester polyol, the polycarbonate polyol and the tackifying resin, and then adding the hydrolysis resistant agent and the catalyst.
The process of the premixing is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
After the premixing is finished, the invention also preferably comprises the step of carrying out vacuum dehydration on the mixed material for 2 hours at the temperature of 120-130 ℃.
After the anti-hydrolysis agent and the catalyst are added, the method also preferably comprises a vacuum stirring process, wherein the vacuum stirring time is preferably 20min, and the rotating speed of the vacuum stirring is preferably 40-80 r/min.
After the vacuum stirring is completed, the invention also preferably comprises temperature reduction, and the target temperature of the temperature reduction is preferably 100 ℃.
After the mixing is finished, the invention also preferably comprises filtration, and the filter screen adopted by the filtration is preferably a 400-mesh filter screen.
In the invention, the component A and the component B are independently packaged by adopting a sealed container; the sealed container is preferably a tinplate can; the liner of the tinplate barrel is preferably a PET/Al/CPP three-layer composite packaging bag.
The invention also provides application of the two-component solvent-free reaction type polyurethane hot melt adhesive in the technical scheme in the field of preparation of solar back panels.
In the invention, the method for applying comprises the following steps:
respectively melting the component A and the component B and then mixing to obtain a two-component solvent-free reaction type polyurethane hot melt adhesive;
preheating a substrate, coating the surface of the substrate with the two-component solvent-free reactive polyurethane hot melt adhesive, laminating the substrate with another substrate, and curing to obtain the solar backboard.
In the invention, the melting temperature of the component A and the melting temperature of the component B are preferably 80-100 ℃, more preferably 85-95 ℃ and most preferably 88-92 ℃. In the present invention, the melting is preferably carried out in a melt-extruder.
In the invention, the mass ratio of the component A to the component B is preferably (10-20): 100, more preferably (12-18): 100, most preferably (14-16): 100.
the mixing process is not particularly limited, and may be performed by a method known to those skilled in the art. In the embodiment of the invention, the mixing process is specifically that the output quantities of the component A and the component B are controlled by a metering pump and are conveyed to a static mixing pipe to be mixed, so that the two-component solvent-free reaction type polyurethane hot melt adhesive is obtained. According to the invention, after a substrate is preheated, the surface of the substrate is coated with the two-component solvent-free reactive polyurethane hot melt adhesive, and is pressed with another substrate and then cured to obtain the solar backboard.
In the present invention, the material of the substrate is preferably PET, PVDF, PVF, or PE.
Before preheating the substrate, the invention also preferably comprises corona treatment of the substrate, and the process of the corona treatment is not limited in any way, and can be carried out by adopting a process well known to those skilled in the art and ensuring that the surface tension of the treated film reaches 42 dyne/cm.
In the invention, the preheating temperature is preferably 40-50 ℃, and most preferably 45-50 ℃.
Before coating, the temperature of the double-component solvent-free reactive hot melt adhesive is preferably kept at 80-100 ℃, and more preferably kept at 85-95 ℃.
In the present invention, the coating is preferably roll coating, curtain coating or extrusion coating.
In the invention, the coating amount of the coating is preferably 7-15 g/m, more preferably 8-14 g/m, and most preferably 9-12 g/m.
After the pressing is finished, the invention also preferably comprises the steps of cooling, rolling and standing in sequence; the cooling temperature is preferably 25-30 ℃; the rolling process is not limited in any way, and can be carried out by adopting a process known by a person skilled in the art. In the present invention, the time for the standing is preferably 6 hours.
In the invention, the curing temperature is preferably 45-60 ℃, and more preferably 50-55 ℃; the time is preferably 24 to 48 hours, and more preferably 30 to 40 hours.
The following will explain the two-component solvent-free reactive hot melt adhesive and its application in detail with reference to the examples, but they should not be construed as limiting the scope of the invention.
Example 1
Preparation of component A: adding 3kg of silane coupling agent (CG-0187 from Fukuchen optical chemical Co., Ltd.) into 97kg of HDI trimer (HT 100 from Futai Wanhua company) under stirring, stirring for 30min, and sieving with a 400-mesh sieve to obtain a component A (with the functionality of 3.6 and the mass percentage of isocyanate of 21%);
preparation of the component B: mixing 71kg of polyester polyol (H3020 polyester polyol purchased from Shanghai Crist Engineers, Ltd., hydroxyl value range is 15-30 mgKOH/g), 15kg of polycarbonate polyol (SYHP 1000 polycarbonate polyol purchased from Shanghai Crist Engineers, Ltd.) and 12.98kg of tackifying resin (E-44 epoxy resin purchased from Yueyanite), vacuum dehydrating at 120 ℃ for 2H, adding 1kg of hydrolysis-resistant assistant P200 from German Rhine and 20g of dibutyltin dilaurate (Gaosmidt TMG218), stirring for 20min under vacuum, cooling to 100 ℃, and sieving with 400-mesh filter screen to obtain component B;
respectively putting the component A and the component B into a melt adhesive machine, heating to 90 ℃ for melting, and uniformly mixing the component A and the component B according to the mass ratio of 16:100 to obtain the two-component solvent-free reactive polyurethane hot melt adhesive;
carrying out corona treatment on a PET film substrate, preheating until the surface of the substrate reaches 50 ℃, coating a two-component solvent-free reaction type polyurethane hot melt adhesive with the preheating surface of the PET film substrate at the temperature of 90 ℃, wherein the coating amount is 10 g/square meter, laminating the two-component solvent-free reaction type polyurethane hot melt adhesive with another substrate (made of a PVDF film), rolling, cooling to 25 ℃, standing for 6 hours, and curing at the temperature of 50 ℃ for 36 hours to obtain the solar backboard.
According to the GB/T36802-2018 standard, the performance test is carried out on the two-component solvent-free reaction type polyurethane hot melt adhesive composite back plate, and the test results show that the initial peel strength of the PVDF/PET film after being compounded for 6 hours reaches 6.9N/cm, the peel strength after being cured for 36 hours at 50 ℃ reaches 6.2N/cm, and the peel strength after being aged at the high temperature and the high humidity of 121 ℃ for X48 hours reaches 4.9N/cm', which are obviously higher than the requirements of the national standard GB/T36802-2018.
Example 2
Preparation of component A: under the condition of stirring, adding 2kg of silane coupling agent (purchased from caruncle morning chemical industry Co., Ltd.) into 98kg of HDI trimer (purchased from HT100 of the Tantaowwawa company), stirring for 30min, and sieving with a 400-mesh filter screen to obtain a component A (the functionality is 3.6, and the mass percentage of isocyanate is 21.1%);
preparation of the component B: mixing 72kg of polyester polyol (H3020 polyester polyol purchased from Shanghai Crist Engineers, Ltd., hydroxyl value range of 15-30 mgKOH/g), 13kg of polycarbonate polyol (SYHP 1000 polycarbonate polyol purchased from Shanghai Crist Engineers, Ltd.), and 11.98kg of tackifying resin (E-44 epoxy resin purchased from Yueyanite), vacuum dehydrating at 120 ℃ for 2H, adding 3kg of hydrolysis-resistant assistant P200 from German Rhine and 15g of dibutyltin dilaurate (Gaosmidt TMG218), stirring under vacuum for 20min, cooling to 100 ℃, and sieving with 400 mesh sieve to obtain component B;
respectively putting the component A and the component B into a melt adhesive machine, heating to 90 ℃ for melting, and uniformly mixing the component A and the component B according to the mass ratio of 15:100 to obtain the two-component solvent-free reactive polyurethane hot melt adhesive;
after carrying out corona treatment on a PET film substrate, preheating the PET film substrate until the surface of the substrate reaches 50 ℃, coating a two-component solvent-free reaction type polyurethane hot melt adhesive with the preheating surface of the PET substrate at the temperature of 90 ℃, wherein the coating amount is 10 g/square meter, carrying out lamination with another substrate (made of a PVDF film), rolling, cooling to 25 ℃, standing for 6 hours, and curing at the temperature of 50 ℃ for 36 hours to obtain the solar backboard.
According to the GB/T36802-2018 standard, the performance test is carried out on the two-component solvent-free reaction type polyurethane hot melt adhesive composite back plate, and the test results show that the initial peel strength of the PVDF/PET film after being compounded for 6 hours reaches 6.7N/cm, the peel strength after being cured for 36 hours at 50 ℃ reaches 6.4N/cm, and the peel strength after being aged at the high temperature and the high humidity of 121 ℃ for X48 hours reaches 4.5N/cm', which are obviously higher than the requirements of the national standard GB/T36802-2018.
Example 3
Preparation of component A: under the condition of stirring, adding 1kg of silane coupling agent (purchased from caruncle morning chemical industry Co., Ltd.) into 99kg of HDI trimer (purchased from HT100 of the Tantaowski company), stirring for 30min, and sieving by a 400-mesh filter screen to obtain a component A (the functionality is 3.6, and the mass percentage of isocyanate is 21%);
preparation of the component B: mixing 74kg of polyester polyol (H3020 polyester polyol purchased from Shanghai Crist Engineers, Ltd., hydroxyl value range is 15-30 mgKOH/g), 10kg of polycarbonate polyol (SYHP 1000 polycarbonate polyol purchased from Shanghai Crist Engineers, Ltd.), and 14kg of tackifying resin (E-44 epoxy resin purchased from Yueyang petrochemical), dehydrating in vacuum at 120 ℃ for 2H, adding 1.99kg of hydrolysis-resistant assistant P200 from German Rhine and 10g of dibutyltin dilaurate (Gaosmidt TMG218), stirring in vacuum for 20min, cooling to 100 ℃, and sieving with 400 mesh filter screen to obtain component B;
respectively putting the component A and the component B into a melt adhesive machine, heating to 90 ℃ for melting, and uniformly mixing the component A and the component B according to a mass ratio of 14:100 to obtain the two-component solvent-free reactive polyurethane hot melt adhesive;
after carrying out corona treatment on a PET film substrate, preheating the PET film substrate until the surface of the substrate reaches 50 ℃, coating a two-component solvent-free reaction type polyurethane hot melt adhesive with the preheating surface of the PET substrate at the temperature of 90 ℃, wherein the coating amount is 10 g/square meter, carrying out lamination with another substrate (made of a PVDF film), rolling, cooling to 25 ℃, standing for 6 hours, and curing at the temperature of 50 ℃ for 36 hours to obtain the solar backboard.
According to the GB/T36802-2018 standard, the performance test is carried out on the two-component solvent-free reaction type polyurethane hot melt adhesive composite back plate, and the test results show that the initial peel strength of the PVDF/PET film after being compounded for 6 hours reaches 6.2N/cm, the peel strength after being cured for 36 hours at 50 ℃ reaches 5.9N/cm, and the peel strength after being aged at the high temperature and the high humidity of 121 ℃ for X48 hours reaches 4.3N/cm', which are obviously higher than the requirements of the national standard GB/T36802-2018.
Comparative example
Preparation of component A: passing 100kg of HDI trimer (HT 100 from Tantaowwawa company) through a 400-mesh filter screen to obtain a component A (the functionality is 3.6, and the mass percentage of isocyanate is 21.2%);
preparation of the component B: a solvent type solar backboard composite adhesive D5910A (purchased from Wuhan Dyer science and technology Limited, with a hydroxyl value range of 10-15 mgKOH/g and a solid content of 65%) is filtered through a 400-mesh filter screen to obtain a component B;
uniformly mixing the component A and the component B according to the mass ratio of 6:100 (referring to the recommended proportion of a D5910A product instruction), adding a proper amount of ethyl acetate solvent according to the use requirement, and adjusting the solid content of the working glue solution to 30% to obtain the two-component solvent type polyurethane composite glue;
carrying out corona treatment on a PET film substrate, coating a double-component solvent type polyurethane composite adhesive on the surface of the PET substrate, wherein the coating amount of a dry adhesive is 10 g/square meter, drying at 90-100 ℃, laminating with another substrate (made of a PVDF film), rolling, cooling to 25 ℃, standing for 6 hours, and curing at 50 ℃ for 36 hours to obtain the solar backboard.
According to the GB/T36802-2018 standard, the performance test is carried out on the two-component solvent type polyurethane adhesive composite back plate, and the test results show that the initial peel strength of the PVDF/PET film after 6 hours of compounding reaches 5.1N/cm, the peel strength after 36 hours of curing at 50 ℃ reaches 5.3N/cm, the peel strength after high-temperature high-humidity aging at 121 ℃ for X48 hours reaches the requirement of 4.1N/cm', and the requirements of the national standard GB/T36802-2018 are basically met.
From the test results of the above examples and comparative examples, it can be seen that the two-component solvent-free reactive polyurethane hot melt adhesive obtained by the invention has high peel strength, all meets the requirements of national standard GB/T36802-2018, and is superior to various performance indexes of solvent type solar back panel adhesives commonly used in the existing market. The invention has obvious advantages of environmental protection and safety because no organic solvent is used, is favorable for further popularization and use, and replaces the prior solvent type solar backboard adhesive.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A double-component solvent-free reaction type polyurethane hot melt adhesive is characterized by comprising a component A and a component B which are independently packaged;
the component A comprises a polyurethane prepolymer; the polyurethane prepolymer contains isocyanate;
the component B comprises polyester polyol, polycarbonate polyol and an auxiliary agent; the mass ratio of the polyester polyol to the polycarbonate polyol to the auxiliary agent is (70-80): (7-15): (10-17);
the mass ratio of the component A to the component B is (10-20): 100, respectively;
the two-component solvent-free reaction type polyurethane hot melt adhesive does not contain a solvent.
2. The two-component solvent-free reaction type polyurethane hot melt adhesive as claimed in claim 1, wherein the functionality of the polyurethane prepolymer is not less than 2, and the mass percentage of the isocyanate in the component A is 10-30%.
3. The two-component solvent-free reaction type polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the preparation raw materials of the polyurethane prepolymer comprise polyisocyanate and silane coupling agent;
the mass ratio of the polyisocyanate to the silane coupling agent is (97-100): (0-3).
4. The two-component solvent-free reactive polyurethane hot melt adhesive according to claim 1, wherein the polycarbonate polyol has a number average molecular weight of 500 to 4000;
the hydroxyl value of the polycarbonate polyol is 28-250 mg KOH/g.
5. The two-component solvent-free reactive polyurethane hot melt adhesive of claim 1, wherein the auxiliary agents comprise catalysts, hydrolysis resistance agents and tackifying resins;
the mass ratio of the catalyst to the hydrolysis resistant agent to the tackifying resin is (0.005-2): (0.1-6): (9-14).
6. The two-component solvent-free reactive polyurethane hot melt adhesive according to claim 5, wherein the catalyst comprises an organotin catalyst and/or dimorpholinyldiethylether;
the hydrolysis resistant agent comprises polycarbodiimide;
the tackifying resin comprises an epoxy resin.
7. The application of the two-component solvent-free reactive polyurethane hot melt adhesive as claimed in any one of claims 1 to 6 in the field of preparation of solar back sheets.
8. The application of claim 7, wherein the method of applying comprises the steps of:
respectively melting the component A and the component B and then mixing to obtain a two-component solvent-free reaction type polyurethane hot melt adhesive;
preheating a substrate, coating the surface of the substrate with the two-component solvent-free reactive polyurethane hot melt adhesive, laminating the substrate with another substrate, and curing to obtain the solar backboard.
9. The use according to claim 8, wherein the melting temperatures of the A and B components are independently 80 to 100 ℃.
10. The use according to claim 8, wherein the curing temperature is 45 to 60 ℃ and the curing time is 24 to 48 hours.
CN202111272176.9A 2021-10-29 2021-10-29 Double-component solvent-free reaction type polyurethane hot melt adhesive and application thereof Pending CN113773781A (en)

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