CN107629713B - Photovoltaic module busbar insulating tape, busbar and photovoltaic module containing same - Google Patents

Photovoltaic module busbar insulating tape, busbar and photovoltaic module containing same Download PDF

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Publication number
CN107629713B
CN107629713B CN201710950891.0A CN201710950891A CN107629713B CN 107629713 B CN107629713 B CN 107629713B CN 201710950891 A CN201710950891 A CN 201710950891A CN 107629713 B CN107629713 B CN 107629713B
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insulating
coating
photovoltaic module
resin
adhesive tape
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CN107629713A (en
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邓建波
王善生
宇野敬一
陈洪野
吴小平
高畠博
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Suzhou Competition Application Technology Ltd By Share Ltd
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Priority to PCT/CN2018/100544 priority patent/WO2019072016A1/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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/30—Electrical components
    • H02S40/36—Electrical components characterised by special electrical interconnection means between two or more PV modules, e.g. electrical module-to-module connection
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
    • 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 relates to a photovoltaic module bus bar insulating tape, a bus bar comprising the insulating tape and a photovoltaic module. The raw material formula of the coating comprises fluorocarbon resin containing hydroxyl or amino, filler, auxiliary agent and first curing agent; the raw material formula of the adhesive layer comprises epoxy resin, thermoplastic resin and/or synthetic rubber, a second curing agent and a flame retardant. The coating has excellent adhesion with a base material, the scratching force is still kept at 0-1 level even after the coating is subjected to high temperature and high humidity, and the ultraviolet barrier property of the coating is excellent. The pressure-sensitive adhesive layer has excellent adhesion to a base material layer and also has excellent adhesion to a metal. The insulating tape has the performance of resisting ultraviolet rays, thermal shock, cold and hot shock, damp and hot and the like. The insulating tape is hot-pressed on a metal plate or a metal bus bar and can be used for insulating the photovoltaic module bus bar.

Description

Photovoltaic module busbar insulating tape, busbar and photovoltaic module containing same
Technical Field
The invention belongs to the field of insulating tapes, and relates to a photovoltaic module busbar insulating tape, a busbar comprising the insulating tape and a photovoltaic module.
Background
The photovoltaic module bus bar is used for connecting the cell sheets which are connected together in series. The current technology is that the bus bars and the welding strips led out from the battery pieces are manually welded together, and then the bus bars are separated, insulated and fixed by using insulating isolation films/insulating strips.
In the past, manual welding is adopted for connecting the photovoltaic module bus bar and the cell piece welding strip, so that the efficiency is low; the bus bars are isolated by using a thick insulating film, so that local areas swell, and the flatness of the appearance is influenced; the surface layer of the existing bus bar is exposed in a packaging adhesive film (such as a transparent polyolefin material), and the appearance of the bus bar is irregular in texture and irregular in welding points, so that the aesthetic feeling of the appearance is seriously influenced.
Some improvements are made in the existing patent documents with respect to the bus bars or the insulating films for insulation between the bus bars, as described below.
The bus bar for the photovoltaic module disclosed in the Chinese patent with the publication number of CN 102856415A comprises a substrate, wherein the surface of the substrate is provided with an insulating area and a weldable area; the surface of the insulating area is covered with an insulating material layer, the surface of the weldable area is covered with a weldable layer, and the insulating material layer is made of fluorine film plastic or insulating PET. The bus bar can realize good insulation among the bus bars and between the bus bars and the battery strings under the condition of no additional insulating material and packaging process. However, the adhesion between the fluorine film plastic or the insulating PET and the metal is poor, and the performances of heat shock resistance, moist heat resistance and the like are also poor. Can only meet the requirement of manual welding process, can not be suitable for automatic production, and has lower efficiency.
Chinese patent publication No. CN 103107208A discloses an electrode isolation structure for a solar cell module, which includes a first layer, two second layers and at least one third layer, wherein the two second layers are respectively disposed on both sides of the first layer, the third layer is disposed on at least one of the two second layers, the first layer is made of polyethylene terephthalate, polycarbonate, polyethylene naphthalate, polybutylene terephthalate or polymethyl methacrylate, the second layer is made of ethylene-vinyl acetate copolymer EVA, and the third layer is made of 90-99 wt% of ethylene-vinyl acetate copolymer EVA, 0-5 wt% of an organic ultraviolet absorber, 0-5 wt% of an organic ultraviolet stabilizer and 1-10 wt% of an inorganic ultraviolet resistant material. However, the adhesive force between the insulating strip and the metal welding strip is poor, the heat resistance is poor, the manual welding process can be met, the insulating strip cannot be suitable for automatic production, and the efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a photovoltaic module bus bar insulating tape suitable for automatic welding.
The invention also provides a bus bar containing the insulating tape and a photovoltaic module.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an insulating tape includes an insulating base material layer, a coating layer formed on one surface of the insulating base material layer, and an adhesive layer formed on the other surface of the insulating base material layer.
The coating comprises the following raw materials in percentage by mass:
Figure BDA0001432827200000021
the first curing agent is one or the combination of more than two of isocyanate curing agent, amino resin and anhydride curing agent;
the raw material formula of the adhesive layer comprises the following components in percentage by mass:
Figure BDA0001432827200000022
the adhesive layer of the insulating tape of the invention has excellent adhesion with an insulating base material layer and excellent adhesion with metal, and the insulating tape also has the performance of resisting environmental aging such as ultraviolet rays, thermal shock, cold and hot shock, damp and heat and the like.
Preferably, the insulating base layer may be a polyimide film.
Preferably, the fluorocarbon resin containing hydroxyl in the coating is one or a combination of more than two of tetrafluoroethylene/vinyl ether copolymer, tetrafluoroethylene/vinyl ether monomer copolymer, chlorotrifluoroethylene and vinyl ester copolymer, chlorotrifluoroethylene and vinyl ether copolymer and polyvinylidene fluoride.
Preferably, the isocyanate curing agent in the coating layer is preferably an aliphatic isocyanate or an alicyclic isocyanate, and is a bifunctional or higher isocyanate compound and/or a blocked isocyanate.
Preferably, the auxiliary agent is one or a mixture of two of an epoxy compound and a carbodiimide compound, so that the adhesive force of the coating after moisture and heat resistance can pass a cross-cut test and reach a level of 0-1 grade. The epoxy compound is a hydrogenated epoxy resin, and the hydrogenated epoxy resin refers to a hydrogenated epoxy resin containing two or more epoxy functional groups.
The first feature of the coating of the invention is:the fluorocarbon resin is used as a component A, the isocyanate compound with more than two functions and/or the blocked isocyanate is used as a component B, the epoxy compound with more than two functions is used as a component C, and the weight ratio of A to B is 80/1-30/25, and the weight ratio of A to C is 80/0.1-30/10. The above-mentioned bifunctional isocyanate compound and/or blocked isocyanate component B and the above-mentioned bifunctional epoxy compound component C are effective as a curing agent for the fluorocarbon coating of the present invention, and the polymer of the coating has a new carboxyl group generated by hydrolysis of the urethane bond, and the components B and C have the function of repairing and re-bonding the cleaved urethane chains while suppressing the catalytic action thereof. In addition, the isocyanate compound and the epoxy compound are effective in improving the adhesion between metal and ceramics, and the isocyanate compound and the epoxy compound are also reacted with each other. For these reasons, the whole is designed to contain 1 time or more of the reactive amounts of the B component and the C component as compared with the reactive amount of the fluorocarbon-terminated resin. From the above viewpoint of hydrolysis resistance and the requirement for the coating layer, the A/B (weight ratio) is set to 80/1 to 30/25. If less than 30/25, the fluorocarbon coatingThe adhesion itself to the substrate will be deteriorated.
Also, from the viewpoint of the above-mentioned hydrolysis resistance and the requirement for the coating layer, the A/C (weight ratio) is set to 80/0.1 to 30/10. In other words, once this weight ratio exceeds 80/0.1, a sufficient amount of epoxy groups and carboxyl groups of the fluorocarbon resin cannot be obtained to react; when the weight ratio is less than 30/10, the adhesiveness of the fluorocarbon resin itself is deteriorated. Other compounds (e.g., carbodiimide compounds and oxazoline compounds) which can react with a hydroxyl group and a carboxyl group, such as isocyanate compounds and epoxy compounds, can also be used together.
If the auxiliaries used in the present invention are exemplified, epoxy resins such as hydrogenated bisphenol A type resins, e.g., EP4080E from Ediko, ST3000 from Nissin iron chemical; carbodiimide compounds as Langsheng chemistry
Figure BDA0001432827200000031
Figure BDA0001432827200000032
V-02B, V-04B, V-05 available from Nisshinbo Co.
Examples of the bifunctional or higher isocyanate compound used in the present invention include aliphatic isocyanates and alicyclic isocyanates, for example, 3-functional isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, m-xylylene isocyanate, 4 "-dicyclohexylmethane diisocyanate and adducts derived from diisocyanates thereof, biurets, isocyanurates and the like. As the aromatic isocyanate, there may be mentioned 3-functional isocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate and adducts derived from its diisocyanate, biurets and isocyanurates.
The fluorocarbon coating of the present invention can be produced by selecting an appropriate isocyanate depending on the end use, and in the use where the heat resistance of the binder is particularly required, an isocyanate having 3 or more functional groups is generally used as a crosslinking agent. In the case of applications where both heat resistance and light resistance are particularly required, it is preferable to use an aliphatic isocyanate having 3 or more functions as a crosslinking agent.
The blocked isocyanate used in the present invention is a product of the reaction between the isocyanate and the blocking agent as described above, and examples of the blocking agent include oximes such as formamide oxime, hydroxyacetamidine, ethylamine oxime, acetoxime and methyl ethyl ketoxime, active dimethyl compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate and acetylacetone, phenols such as phenol and cresol, lactams such as caprolactam, alcohols such as 2-ethylhexanol, and amines such as 2, 3-dimethylpyrazole. Among them, oximes, lactams, and amines are satisfactory blocking agents.
The dissociation temperature of the blocked isocyanate is preferably between 90 ℃ and 200 ℃, more preferably between 90 ℃ and 150 ℃. When the temperature is lower than 90 ℃, the adhesive may be dissociated during the drying of the adhesive solvent and the adhesiveness may be deteriorated, and when the temperature exceeds 200 ℃, the laminated plastic film may be deteriorated.
In the present invention, 2 or more types of bifunctional or more isocyanate compounds and/or blocked isocyanates can be used in combination. In the case where an isocyanate and a blocked isocyanate are used simultaneously, the amount of the blocked isocyanate used is 20% to 100% by weight based on the total weight of the both, which is a highly desirable embodiment of the present invention. The curing characteristics and long-term stability of the adhesive can be compromised.
The filler in the coating is one or the combination of more than two of titanium dioxide, graphite, carbon black, barium sulfate and silicon oxide.
Second feature of the coating of the inventionThe fluorocarbon resin is used as a component A, the filler (one or a combination of more than two of titanium dioxide, graphite, carbon black, barium sulfate and silicon oxide) is used as a component D, and the A/D (weight ratio) is 80/5-30/60, and the preferable range is 80/10-30/30; if higher than 80/5, the laminate of the coating layer and the polyimide film does not exhibit a complete ultraviolet-ray blocking effect; if the amount is less than 30/60, the adhesion between the coating layer and the substrate is poor.
When the titanium dioxide used in the present invention is exemplified, the rutile type is classified into a rutile type and an anatase type, and the rutile type is compared with the anatase type, and since a unit lattice thereof is composed of two titanium dioxide molecules and the anatase type is composed of four titanium dioxide molecules, the unit lattice thereof is small and compact, and thus has large stability and relative density, and thus has a high refractive index and dielectric constant and low thermal conductivity. Therefore, the rutile type titanium dioxide is preferred in the invention, and the preferred range of the particle size is 0.1-2 um. More preferably between 0.2 and 1 um. Such as R900, R960, R101, R103, R706, etc. from DuPont; r405, R420, RD3, etc. from Shaharley corporation; CR-50, CR-57, CR-super70 and the like of the Japan stone industry.
Preferably, the graphite and/or carbon black used in the present invention refers to graphite and/or carbon black which is subjected to oxidation treatment, and has relatively excellent insulation property and dispersibility in polymers. Such as Special black4,4A,5,640, etc. from Orion, Empersor 1200, Empersor 1600, etc. from Kabot.
Preferably, the specific nanoscale barium sulfate used in the present invention has a particle size distribution D50 < 0.8um, preferably D50 < 0.5 um. The filler has a particle size distribution D50 of more than 0.8um, and has poor shielding property and ultraviolet resistance effect on the coating.
Preferably, the silica used in the present invention particularly refers to a silica prepared by vapor deposition of an amorphous structure, and has excellent dispersibility and thickening effect through organic surface treatment. The silica compounds are ACEMATT HK400, ACEMATT HK450, ACEMATT HK460, ACEMATT OK412, ACEMATT OK500, ACEMATT OK520, ACEMATT OK607, ACEMATT OK412LC and Degussa
Figure BDA0001432827200000041
Figure BDA0001432827200000042
Etc., Grace's C803, C805, C807, C809, C7000, CP4-8991, etc.
A third feature of the coating of the present invention is thatThe thickness range of the coating is 1-20 um, if the thickness is less than 1um, the ultraviolet (280-400 nm) blocking rate of the coating cannot be more than 90%, if the thickness is more than 20um, the coating can have certain reverse viscosity, and no economic benefit exists. The preferable coating thickness range is 1-15 um.
Preferably, the raw material formula of the coating further comprises 0.01-2% of a curing accelerator of hydroxy fluorocarbon resin and 0.1-2% of a dispersing agent. The curing accelerator can be one or more of tertiary amine catalyst (including quaternary ammonium salt) and organic metal compound. The dispersant may be one or a combination of several of polyvalent carboxylic acid dispersant, silane coupling agent dispersant, silicate dispersant, silica compound, and the like.
The first feature of the epoxy adhesive layer of the present invention is thatThe addition amount of the thermoplastic resin and/or the synthetic rubber is 10-50%, if the addition amount is less than 10%, the tackifying effect of the adhesive layer on the film and the metal plate is not obvious, the toughening effect is not achieved, and the adhesive layer is hard on the whole; if the amount of the additive is more than 50%, the glass transition temperature of the adhesive layer is lowered more, which affects the heat resistance of the adhesive layer.
The epoxy resin used in the present invention is exemplified by bisphenol a type, bisphenol S type, bisphenol F type, novolac epoxy, biphenyl type, phenol type, and one or a combination of two of hydride thereof and aliphatic epoxy thereof. The compound having 2 epoxy groups or 3 or more epoxy groups in the epoxy resin molecule is not limited herein, but may be an epoxy resin modified by organosilicon, carboxyl-terminated butadiene-acrylonitrile rubber (CTBN), acrylic acid, polyurethane, or polyamide, or an epoxy resin molecule segment containing a flame-retardant bromine element, phosphorus element, sulfur element, or nitrogen element.
The resin having 2 epoxy functional groups on the molecular chain is selected from bisphenol A type, bisphenol F type, bisphenol S, stilbene type epoxy resin, alicyclic type epoxy resin, biphenyl type epoxy resin. Non-brominated epoxy resins, commercially available resins such as JER828, JER871, JER1001 (Mitsubishi chemical), ELA115 of Sumitomo chemical industry, ELA127, NC-3000H of Nippon Chemicals, etc., brominated epoxy resins such as jER5050, jER5048, jER5046 (Mitsubishi chemical).
Resins having 3 epoxy functional groups in the molecular chain, such as phenol type epoxy, o-cresol type epoxy, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, commercially available NPPA-431A70, NPPN631, NPPN638, such as from south Taiwan Asia. EOCN-1020, XD-1000, NC-2000, NC-3000, EPPN-500 of Japan Chemicals.
The epoxy resin with 2 epoxy groups in the molecular weight has better effect on flexibility and bonding strength after being cured; epoxy resins having 3 or more epoxy groups in the molecular weight are effective in improving heat resistance and glass transition temperature of the cured resin. In view of the above characteristics, the epoxy resin used in the present invention may be one of the epoxy resins or a mixture of two or more of the epoxy resins.
Preferably, various commercially available thermoplastic resins can be used as the thermoplastic resin, and suitable thermoplastic resins are polyester resins, acrylic resins, phenoxy resins, and polyamideimide resins. Optionally phenoxy resin PPO x MX-90(SABICINNOVATIVE PLASTICS), PKHA available from Inchem Corp. Inc., PKHB, PKHB +, PKHC, PKHH, 1256, 4250, 4275 available from Mitsubishi chemical corporation, etc.; polyamide-imide resins Nippon Kayaku co., Ltd. company's Kayaflex series and epoxy-containing acrylic resins such as Hitachi Chemical co., Ltd.
Preferably, the synthetic rubber is one or a mixture of two of acrylic rubber and nitrile rubber. The glass transition temperature range of the rubber is between-50 ℃ and-10 ℃. Acrylic rubber such as ethylene acrylic rubber from DuPont
Figure BDA0001432827200000061
Series, e.g.
Figure BDA0001432827200000062
VMX4017, VMX5015V, and the like, nitrile rubbers such as JSRJSR-XER32, JSR-XER91, and the like, of south Taiwan chemical industry Co., Ltd
Figure BDA0001432827200000063
Series, such as 1072, 1072CG, 3245C, etc.
The second feature of the adhesive layer of the present invention is thatThe usage amount of the second curing agent is 0.1-10%, and if the usage amount is less than 0.1%, the crosslinking degree of the adhesive layer is not high, and the heat resistance is not good; if the content is more than 10%, the degree of crosslinking is too high, which means that the adhesive layer is hard and the adhesive force is affected.
The present invention is not particularly limited in the use of the second curing agent, and any material commonly used as a curing agent for epoxy resins may be used, and polyamine-based curing agents and anhydride-based curing agents are preferred. The polyamine-based curing agent may be selected from m-phenylenediamine, m-xylylenediamine, diaminodiphenyl sulfone, phenylenediamine, diaminodiphenylmethane, dicyandiamide, and polyamide curing agent. As the curing agent based on an acid anhydride, phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, etc. can be selected. The above-mentioned curing agents may be used singly or in combination of two or more kinds.
The adhesive layer of the present invention may be further modified as follows: 0.01-1% of a curing agent accelerator is added to accelerate the reaction between the epoxy resin and the second curing agent. The curing agent accelerator of the present invention may be any one or a mixture of two or more of the existing curing agent accelerators in the prior art, preferably imidazole compounds, triorganophosphine compounds, quaternary ammonium salts, fluoroborate salts, and the like. As the imidazole compound, 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 2-undecylimidazole (C11Z), 1-cyanoethyl-2-undecylimidazole (C11Z-CN) and 2-heptadecylimidazole (C17Z) are preferably used, and each of the above imidazole compounds may be used alone or in combination of two or more kinds. As the triorganophosphine compound, triphenylphosphine, tributylphosphine, or the like is preferably used. As the quaternary ammonium salt, a tris (diethylacetate) salt of 2, 4, 6-tris (dimethylaminomethyl) phenol, a tris (oleate) salt of 2, 4, 6-tris (dimethylaminomethyl) phenol, or the like can be preferably used. The fluoborate can be selected from one or a mixture of more than two of a complex of boron trifluoride and monoethylamine, a complex of boron trifluoride and n-butylamine, a complex of boron trifluoride and benzylamine, a complex of boron trifluoride and dimethylaniline and the like.
The third feature of the adhesive of the present invention is thatThe addition amount of the flame retardant is 10-70%, if the addition amount is less than 10%, the flame retardant performance of the adhesive tape cannot reach the V-2 grade, and if the addition amount is more than 70%, the adhesive performance of the adhesive layer is affected, and the adhesive tape is not easy to disperse in glue water, so that the coating effect is affected. Preferably 20 to 60%.
Preferably, the flame retardant is one or a mixture of more of a bromine (Br) -based flame retardant, a chlorine (Cl) -based flame retardant, a phosphorus (P) -based flame retardant, a nitrogen (N) -based flame retardant, a silicon (Si) -based flame retardant, a metal hydroxide-based flame retardant, a metal oxide flame retardant, a metal boride flame retardant, and the like. Among them, preferred is one or a mixture of several of phosphorus (P) -based flame retardants, nitrogen (N) -based flame retardants, silicon (Si) -based flame retardants, metal hydroxide-based flame retardants, metal oxide flame retardants, metal boride flame retardants, and the like.
As an example of the phosphorus-containing flame retardant used in the present invention, an organic phosphide such as a phenol-based azo-phosphate oligomer (FP110) or the like; organic phosphonates, condensed halogen-free phosphates, tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, butylbenzene-based phosphates, propylbenzene-based phosphates, phenoxy polyphosphazene, dimethyl methylphosphonate, diethyl ethylphosphonate, isopropylphenyl phosphate, tert-butylphenyl diphosphate, tetraarylarylene-bis-phosphate, resorcinol phosphate, tetraphenyl bisphenol a-diphosphate, pentaerythritol melamine phosphate, and the like; and phosphonites, such as alkali metal phosphonites: sodium or potassium phosphinate, ammonium polyphosphate, aluminum diethylphosphinate, zinc diethylphosphinate, and the like.
If the nitrogen-containing flame retardant used in the present invention is exemplified by a nitrogen-containing flame retardant having a nitrogen content in the range of 15 to 30 mass%, a nitrogen-containing flame retardant having a nitrogen content in the range of 15 to 25 mass% is preferable. Preferred nitrogen-containing polyphosphate compounds of the present invention are, for example: melamine polyphosphate (MPP), ammonium polyphosphate, melamine phosphate, melamine cyanurate complex, piperazine polyphosphate, or mixtures thereof. Specific examples are melamine pyrophosphate, melamine triphosphate, melamine pentaphosphate, piperazine pyrophosphate, piperazine triphosphate and piperazine pentaphosphate.
If the silicon flame retardant used in the present invention is exemplified, the silicon flame retardant may be an inorganic silica flame retardant or an organic silicon flame retardant, and the inorganic silica flame retardant includes white carbon black, wollastonite, mica, kaolin, montmorillonite, talc powder, etc.; the organic silicon flame retardant comprises organic siloxane, organic silicon epoxy resin, silicon rubber, cage-like silsesquioxane modified polymer and the like.
The metal hydroxide flame retardant comprises aluminum hydroxide or magnesium hydroxide and the like.
The metal oxide includes antimony trioxide, antimony oxide, iron oxide, tin oxide, and the like.
The metal boride flame retardant comprises zinc borate, barium borate and the like.
The adhesive layer of the invention can also be added with a proper amount of dispersant of 0.01-2%, which is beneficial to improving the compatibility between the flame-retardant filler and the resin, and the dispersant can be one or the combination of a plurality of multivalent carboxylic acid dispersant, coupling agent dispersant, silicate dispersant, silicon dioxide compound and the like. The preferable coupling agent is one or a combination of more of a titanate coupling agent, an aluminate coupling agent, an organosilane coupling agent, an organic chromium complex coupling agent, a borate coupling agent and a silicon dioxide compound, and the more preferable coupling agent type dispersing agent is one or a combination of more of a titanate coupling agent, an aluminate coupling agent and an organosilane coupling agent.
Such as isopropyltris (dioctylpyrophosphate) titanate, isopropyltris (dioctylphosphonoate) titanate, isopropyldioleate acyloxy (dioctylphosphonoate) titanate, monoalkoxy unsaturated fatty acid titanate, chelate of bis (dioctyloxypyrophosphate) ethylene titanate and triethanolamine, bis (dioctyloxypyrophosphate) ethylene titanate, and the like.
Examples of the aluminate coupling agent include an aluminum titanium complex, isopropyl bis (acetoacetato) aluminate, diisopropyl bis (acetylacetonato) aluminate, isopropyl distearoyloxy aluminate and isopropyl distearoyloxy aluminate.
Such as aminosilane, epoxysilane, methacryloxysilane, vinylsilane, alkylsilane, sulfur-containing silane, phenoxysilane, isocyanatosilane, fluorosilane, etc.
The invention can also be added with a proper amount of antioxidant, and the addition amount of the antioxidant is 0.01-3%. The antioxidant is preferably a polyhydric hindered phenol type antioxidant, such as an antioxidant lrganox1010 (pentaerythritol tetrakis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), a phosphite antioxidant 168, a phosphite antioxidant 626, or the like, or a mixture thereof.
According to a preferred aspect of the present invention: the raw material formula of the adhesive layer comprises the following components:
Figure BDA0001432827200000081
the invention also provides a photovoltaic module bus bar which comprises a first insulating adhesive tape, a metal layer and a second insulating adhesive tape which are sequentially stacked, wherein the first insulating adhesive tape and/or the second insulating adhesive tape are/is the insulating adhesive tape, and the adhesive layer of the insulating adhesive tape is bonded with the metal layer.
The invention also provides a photovoltaic module, and the bus bar used by the photovoltaic module comprises the photovoltaic module bus bar.
Due to the application of the technical scheme, compared with the prior art, the invention has lower cost.
The coating disclosed by the invention has excellent adhesion with polyimide, the scribing force is still kept at 0-1 level even after the coating is subjected to high temperature and high humidity, and the ultraviolet barrier property of the coating is excellent.
The adhesive layer of the insulating tape of the invention adopts specific epoxy resin with specific content, and thermoplastic resin and/or synthetic rubber as well as curing agent and flame retardant with specific content are added, so that the prepared adhesive layer not only has excellent adherence with the insulating substrate layer, but also has excellent adhesiveness with metal.
The insulating tape has the performance of resisting ultraviolet rays, thermal shock, cold and hot shock, damp and hot and the like. The insulating adhesive tape provided by the invention is hot-pressed on a metal plate or a metal bus bar, and can be used for insulating the photovoltaic module bus bar.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to specific examples.
1、Preparation of insulating adhesive tape
Dissolving 50% of hydroxy fluorocarbon resin by mass in butyl acetate (or common ethyl acetate, acetone, toluene, xylene, N-dimethylformamide and the like) solvent, adding hydrogenated epoxy resin, carbon black filler and a dispersant BYK9076, and performing dispersion and sanding treatment. Adding an isocyanate curing agent and a dibutyltin dilaurate curing accelerator, uniformly stirring, uniformly coating a coating with the thickness of 5 microns on the polyimide film (PI), heating and evaporating the solvent at the temperature rising speed of 150 ℃/5m ins, and then rolling for later use.
Dissolving 20% of epoxy resin, thermoplastic resin and/or synthetic rubber in 20% of butanone (or common acetone and toluene) and dissolving in 20% of butanone (or common acetone, toluene, xylene, N-dimethylformamide and the like) solvent, adding a flame retardant into the resin solution, and performing dispersion and sanding treatment. Then adding a second curing agent and a curing accelerator, and uniformly stirring. And (3) uniformly coating an adhesive with the thickness of 25 micrometers on the other surface of the polyimide film (PI) with the coating, heating and evaporating the solvent at the heating speed of 100 ℃/5m ins to dry, compounding a release film or release paper, and rolling to obtain the insulating tape.
The above coating and adhesive are preferably subjected to a surface treatment such as corona treatment or plasma treatment on the polyimide film in advance after coating.
2. Preparation of bus bars
Placing a flat tinned copper strip (with the glue surface facing the tinned copper strip) on the coated PI insulating tape, then placing another symmetrical PI insulating tape (with the glue surface facing the tinned copper strip) on the copper strip, rolling at high temperature of 180 ℃/0.2 Mpa/2-3S to prepare a photovoltaic Bus bar (Bus bar), and curing and crosslinking at 80-160 ℃ for 1-2 hours.
Adhesive layer and raw material formulations of the preparation examples, comparative examples, and properties of the insulating tape and the photovoltaic module bus bar manufactured therefrom are shown in tables 1 and 2, and the amounts of the respective components in tables 1 and 2 are in parts by weight.
Table 1 shows the raw material formulations of the adhesive layers of the insulating tapes of examples 1 to 6, and the evaluation results of the properties of the insulating tapes and the photovoltaic module bus bars produced therefrom
Figure BDA0001432827200000091
Figure BDA0001432827200000101
Table 2 shows the raw material formulations of the adhesive layers of the insulating tapes of comparative examples 1 to 7, and the results of evaluating the properties of the insulating tapes and the photovoltaic module bus bars produced therefrom
Figure BDA0001432827200000102
Figure BDA0001432827200000111
The results of the evaluations in tables 1 and 2 include some performance evaluations of the dielectric tape and of the photovoltaic bus bars (bus-bar) made with the dielectric tape. Raw materials in table 1 and table 2:
raw materials in table 1 and table 2:
GK570 fluorocarbon resin, Japan Dajin Fumigation chemical industry Co., Ltd
TPA 100: polyisocyanate curing agent, Asahi Kasei Co Ltd
Special black4 carbon Black, European Dailong, Germany
BYK-9076 dispersant, Bike Germany
EP4080E hydrogenated bisphenol A epoxy resin, Ediko
DBTDL dibutyltin dilaurate
JER-828 bisphenol A epoxy resin, Mitsubishi chemical
XD-1000: poly [ (phenylglycidyl ether) -CO-dicyclopentadiene ], Nippon Chemicals Co., Ltd
XER-32 Nitrile Butadiene Rubber (NBR), JSR Japan K.K.
Figure BDA0001432827200000112
Acrylic rubber, DuPont USA
PX 200: the polycondensation type halogen-free phosphate ester is Nippon Daba chemical;
MC 6000: melamine cyanurate, commodity chemistry;
DICY dicyandiamide, Ningxia Jia peaking chemical Co Ltd
3. Evaluation results of comprehensive Properties
◎, representing the optimal comprehensive performance, ○, representing the performance OK, which can meet the use requirement;
△, the performance was poor, and X, the performance was very poor.
4. Method for evaluating items as described above
(1) Thickness of
The thickness of the coating and adhesive layers was measured with a ten-thousandth micrometer.
(2) Coating griping force
The adherence between the coating and the insulating layer is classified into 0-5 grade by using 3M adhesive tape according to the standard of GB/T9286-1998.
(3) Light blocking ratio (280 to 1100nm)
The test was carried out using a Shimadzu UV-3600 spectrophotometer.
(4) Adhesive strength
The insulating tape and the tinned copper tape are pressed at a high temperature of 150-180 ℃/0.5-2 Mpa/0.5-2 hrs, and then cured and crosslinked at 80-160 ℃ for 1-2 hours. And (4) returning to the room temperature of 25 ℃, and after 20 minutes, testing the bonding strength between the insulating tape and the tinned copper tape, wherein the unit is N/5mm, and according to the standard, the test is carried out at an angle of 180 degrees, and the stripping speed is 100 mm/min.
(5) Thermal shock resistance
And (3) placing a flat tinned copper strip (with the glue surface facing the tinned copper strip) on the coated PI insulating tape, then placing another symmetrical PI insulating tape (with the glue surface facing the tinned copper strip) on the copper strip, pressing at a high temperature of 150-180 ℃/0.5-2 Mpa/0.5-2 hrs, and curing and crosslinking at 80-160 ℃ for 1-2 hours. Namely, photovoltaic Bus bar (Bus bar) is manufactured, and the edge is sealed by about 3 mm. The bus bar manufactured by the method is placed in an environment with the temperature of 200 ℃ and stays for 10s, then the temperature is restored to the room temperature, and the defects of air bubbles, delamination, shrinkage and the like between the insulating tape and between the insulating tape and the tinned copper strip are observed. And if the appearance is not changed, the result is OK, otherwise, the result is NG.
(6) Resistance to cold and hot cycles
Sample preparation is carried out in the same way, the sample is placed in a cold-hot circulating box, circulation is carried out for 40-105 ℃/200 times, the temperature is kept at the constant temperature of 40 ℃/1H, the temperature is increased to 105 ℃/0.5H from 40 ℃/105 ℃/1H, the temperature is reduced to-40 ℃/0.5H from 105 ℃, and the circulation is carried out for 3 hours. And (4) observing whether the insulation tapes and the tinned copper strips have defects of air bubbles, delamination, shrinkage and the like after cold and hot circulation. And if the appearance is not changed, the result is OK, otherwise, the result is NG.
(7) Resistance to wet heat aging
The sample preparation is the same as that of the sample, the sample is placed in a high-temperature high-humidity environment box, the temperature is 85 ℃ multiplied by 85% RH multiplied by 1000H, no air bubble, delamination or shrinkage exists between the insulating tape and the insulating tape after the humid heat aging, no change exists between the insulating tape and the tinned copper strip, the sample is OK if the appearance is not changed, and the sample is NG if the appearance is not changed.
(8) Flame retardancy
The coated tape was sampled in a size of 125mm in length by 13mm in width and fired according to UL 94 standard. And judging the flame retardant grade according to the standard.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. An insulating tape is characterized by comprising an insulating base material layer, a coating layer formed on one surface of the insulating base material layer and an adhesive layer formed on the other surface of the insulating base material layer;
the coating comprises the following raw materials in percentage by mass:
30-80% of fluorocarbon resin containing hydroxyl or amino;
5-60% of a filler;
0.1-10% of an auxiliary agent;
1-25% of a first curing agent;
the first curing agent is an isocyanate curing agent;
the raw material formula of the adhesive layer comprises the following components in percentage by mass:
20-60% of epoxy resin;
5-50% of thermoplastic resin and/or synthetic rubber;
0.1-10% of a second curing agent;
10-70% of flame retardant.
2. The insulating adhesive tape according to claim 1, wherein: the auxiliary agent is one or a mixture of two of an epoxy compound and a carbodiimide compound, so that the adhesive force of the coating after moisture and heat resistance can pass a cross-cut test and reach a level of 0-1 grade.
3. The insulating adhesive tape according to claim 1, wherein: the fluorocarbon resin is one or a composition of more than two of tetrafluoroethylene/vinyl ether copolymer, tetrafluoroethylene/vinyl ether monomer copolymer, chlorotrifluoroethylene and vinyl ester copolymer, chlorotrifluoroethylene and vinyl ether copolymer and polyvinylidene fluoride.
4. The insulating adhesive tape according to claim 1, wherein: the filler is one or the combination of more than two of titanium dioxide, nano-scale graphite, carbon black, barium sulfate and silicon oxide.
5. The insulating adhesive tape according to claim 1, wherein: the raw material formula of the coating also comprises 0.01-2% of a curing accelerator of hydroxyl fluorocarbon resin and 0.1-2% of a dispersing agent.
6. The insulating adhesive tape according to claim 1, wherein: the epoxy resin is bisphenol A type, bisphenol S type, bisphenol F type, novolac epoxy, biphenyl type, phenol type, and one or two of hydride and aliphatic epoxy thereof.
7. The insulating adhesive tape according to claim 1, wherein: the thermoplastic resin is one or the combination of more than two of polyester resin, acrylic resin, phenoxy resin and polyamide-imide resin; the synthetic rubber is one or the combination of two of acrylic rubber and nitrile rubber containing terminal carboxyl.
8. The insulating adhesive tape according to claim 1, wherein: the second curing agent adopts a polyamine-based curing agent and/or an anhydride-based curing agent, and the raw material formula of the adhesive layer further comprises 0.01-2% of a curing accelerator of epoxy resin.
9. The utility model provides a photovoltaic module busbar, includes first insulating tape, metal level and the insulating tape of second that stacks gradually the setting, its characterized in that: the first insulating adhesive tape and/or the second insulating adhesive tape is/are the insulating adhesive tape of any one of claims 1 to 8, and the adhesive layer of the insulating adhesive tape is bonded to the metal layer.
10. A photovoltaic module using a bus bar comprising the photovoltaic module bus bar of claim 9.
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CN109652984B (en) * 2018-12-12 2021-07-20 太仓宝霓实业有限公司 Fabric flame-retardant coating finishing agent composition and preparation method thereof
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