CN107629713A - A kind of photovoltaic module busbar insulating tape, busbar and photovoltaic module comprising the insulating tape - Google Patents

A kind of photovoltaic module busbar insulating tape, busbar and photovoltaic module comprising the insulating tape Download PDF

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Publication number
CN107629713A
CN107629713A CN201710950891.0A CN201710950891A CN107629713A CN 107629713 A CN107629713 A CN 107629713A CN 201710950891 A CN201710950891 A CN 201710950891A CN 107629713 A CN107629713 A CN 107629713A
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China
Prior art keywords
insulating tape
busbar
resin
coating
curing agent
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CN201710950891.0A
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CN107629713B (en
Inventor
邓建波
王善生
宇野敬
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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Suzhou Competition Application Technology Ltd By Share Ltd
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Priority to CN201710950891.0A priority Critical patent/CN107629713B/en
Publication of CN107629713A publication Critical patent/CN107629713A/en
Priority to PCT/CN2018/100544 priority patent/WO2019072016A1/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02Copolymers with acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/25Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02SGENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S40/00Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
    • H02S40/30Electrical components
    • H02S40/36Electrical components characterised by special electrical interconnection means between two or more PV modules, e.g. electrical module-to-module connection
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00Adapting or protecting infrastructure or their operation
    • Y02A30/14Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention relates to a kind of photovoltaic module busbar insulating tape, busbar and photovoltaic module comprising the insulating tape, insulating tape includes insulated base material layer, the coating formed on insulating substrate is laminated and forms the adhesive phase on the another side of insulated base material layer.The composition of raw materials of coating includes fluorocarbon resin, filler, auxiliary agent, the first curing agent of hydroxyl or amino;The composition of raw materials of adhesive phase includes epoxy resin, thermoplastic resin and/or synthetic rubber, the second curing agent, fire retardant.The coating has excellent adherence with base material, still keeps 0 ~ 1 grade even in drawing Gree after hot and humid, the UV separation of coating is outstanding.The adhesive phase not only has excellent adherence with substrate layer, also has excellent cohesive with metal.Insulating tape has the performance of the environmental aging such as uvioresistant, heat shock resistance, thermal shock, damp and hot.By the insulating tape hot pressing on metallic plate or metal bus bars, the insulation available for photovoltaic module busbar.

Description

A kind of photovoltaic module busbar insulating tape, the busbar comprising the insulating tape and Photovoltaic module
Technical field
The invention belongs to insulating tape field, is related to a kind of photovoltaic module busbar insulating tape, comprising the insulating tape Busbar and photovoltaic module.
Background technology
Photovoltaic module busbar is used to each cell piece being cascaded being connected with each other.Adopt the technology that elder generation at present Busbar is linked together with the welding manual welding drawn on cell piece, then between busbar using be dielectrically separated from film/ Insulation strip is separated, and is insulated, fixed.
What the connection between past photovoltaic module busbar and cell piece welding was taken is manual welding, efficiency comparison It is low;Isolated between busbar and busbar using the thick dielectric film of glue so that regional area is heaved, and influences the smooth of outward appearance Degree;Existing busbar top layer is exposed in packaging adhesive film (such as transparent polyolefine material), and some apparent are irregular Texture and irregular pad, have a strong impact on the aesthetic feeling of outward appearance.
In existing patent document for busbar or the dielectric film for being insulated between busbar carried out some improvement, As described below.
A kind of photovoltaic module busbar disclosed in Publication No. CN 102856415A Chinese patent, including base material, base Material surface has insulation layer and solderable area;Insulation layer surface is covered with insulation material layer, and solderable area surface is covered with solderable layer, Insulation material layer is fluorine film plastics or insulation PET.The busbar can be real under conditions of without extra insulation material and packaging technology Good insulation between existing busbar, between busbar and battery strings.It is but viscous between fluorine film plastics or insulation PET and metal Knot power is poor, and the performance such as heat shock resistance, damp and hot is also poor.Manual welding technique can only be met, it is impossible to suitable for automated production, effect Rate is relatively low.
Publication No. CN 103107208A Chinese patent discloses a kind of electrode isolation knot for solar cell module Structure body, the electrode isolation structure include first layer, two second layers and at least one third layer, and two second layers are set respectively In the both sides of first layer, third layer is arranged at least one in two second layers, and first layer is by poly terephthalic acid second two Alcohol ester, makrolon, PEN, polybutylene terephthalate (PBT) or polymethyl methacrylate are made, The second layer is made up of ethylene-vinyl acetate copolymer EVA, and third layer is by 90~99wt% ethylene-vinyl acetate copolymers EVA, 0~5wt% organic uv absorbers, 0~5wt% organic UV stabilizers and the inorganic uvioresistants of 1~10wt% Material is made.But the cohesive force between the insulation strip and metal welding band is poor, heat resistance is bad, can only meet manual welding work Skill, it is impossible to less efficient suitable for automated production.
The content of the invention
A kind of photovoltaic module suitable for automatic welding is provided the invention aims to overcome the deficiencies in the prior art Busbar insulating tape.
The present invention also provides a kind of busbar and photovoltaic module for including above-mentioned insulating tape.
To reach above-mentioned purpose, the technical solution adopted in the present invention is:
A kind of insulating tape, including the coating and formation of insulated base material layer, formation on the insulating substrate is laminated exist Adhesive phase on the another side of the insulated base material layer.
Based on weight/mass percentage composition, the composition of raw materials of described coating includes following component:
First curing agent be in Isocyanates curing agent, amino resins, acid anhydride type curing agent one or two with On combination;
Based on weight/mass percentage composition, the composition of raw materials of described adhesive layer includes following components:
The adhesive phase of insulating tape of the present invention not only has excellent adherence with insulated base material layer, also has with metal Excellent cohesive, insulating tape also have the performance of the environmental aging such as uvioresistant, heat shock resistance, thermal shock, damp and hot.
Preferably, the insulated base material layer can be Kapton.
Preferably, the fluorocarbon resin of hydroxyl is the copolymer of tetrafluoroethylene/ethylene base ether, tetrafluoro second in the coating Copolymer, CTFE and the vinyl ester copolymer of alkene/vinyl ether monomers, CTFE and vinyl ethers copolymerization Composition more than one or both of thing, Kynoar.
Preferably, the Isocyanates curing agent described in the coating, preferably fat race isocyanates or alicyclic Isocyanates, and be more than difunctionality isocyanate compound and/or blocked isocyanate.
Preferably, described auxiliary agent is the mixture of one or both of epoxide, carbodiimide compound, Coating adhesive force after wet-heat resisting is allowd by hundred lattice cross-over experiments and to reach 0~1 grade of level.The epoxidation Compound is hydrogenated epoxy resin, and the hydrogenated epoxy resin refers to the hydrogenated epoxy tree containing two epoxy-functionals and the above Fat.
The fisrt feature of coating of the present invention is:Using above-mentioned fluorocarbon resin as component A, by isocyanic acid more than difunctionality Ester compounds and/or blocked isocyanate are B component, and using epoxide more than difunctionality as C components, and A/B is (heavy Measure ratio) it is 80/1~30/25, A/C (weight ratio) 80/0.1~30/10.More than difunctionality isocyanate compound and/or envelope Epoxide C components more than closed form isocyanates B component, difunctionality, except the curing agent as fluororine-carbon coating of the present invention Beyond playing a role, the polymer of coating because with ammonia ester bond hydrolysis and caused by new carboxyl, B and component C suppressing its catalysis While effect with repair and make between the polyurethane chain cut off further in conjunction with function.In addition, isocyanate compound And epoxide also has certain effect, isocyanate compound and epoxy in terms of the cohesive of metal and ceramics is improved It can also be reacted between compound.For these reasons, with hold fluorocarbon resin reacting dose compared with, by global design into containing The B component and C components of more than 1 times superfluous functional group reactionses amount.Requirement according to the viewpoint of above hydrolytic resistance and to coating, will A/B (weight ratio) is set as 80/1~30/25.If during less than 30/25, fluororine-carbon coating will be broken with the cohesive of base material in itself It is bad.
Equally, the requirement according to the viewpoint of above-mentioned hydrolytic resistance and to coating, A/C (weight ratio) is set as 80/0.1~ 30/10.In other words, the epoxy radicals of sufficient amount and the carboxyl hair of fluorocarbon resin can not be obtained once this weight is than more than 80/0.1 Raw reaction;And in the case that weight ratio is less than 30/10, the cohesive of fluorocarbon resin in itself can be destroyed again.It can also use simultaneously Other compounds that can be reacted as isocyanate compound, epoxide with hydroxyl and carboxyl are (for example, carbonization Diimine compounds, oxazoline compounds).
If the illustration present invention is the auxiliary agent used, epoxy resin such as hydrogenation type bisphenol A type resin, such as Ai Dike strain formulas The EP4080E of commercial firm, the ST3000 of Nippon Steel's chemistry;Carbodiimide compound is such as bright Sheng chemistry The V-02B of Nisshinbo Co., Ltd., V-04B, V-05.
If illustrating isocyanate compound more than difunctionality used in the present invention, in aliphatic isocyanates or What can be enumerated in terms of alicyclic isocyanate has hexamethylene diisocyanate, IPDI, an xyxylene Addition species that isocyanates, 4,4 "-dicyclohexyl methyl hydride diisocyanate and its diisocyanate derive, biuret class, The functional isocyanate of isocyanuric acid esters etc. 3.On aromatic isocyanate, can enumerate have 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 4,4 '-'-diphenylmethane diisocyanate, 1,5- naphthalene diisocyanates and its diisocyanate derive 3 functional isocyanates such as the addition species that go out, biuret class, isocyanuric acid esters.
On the fluororine-carbon coating of the present invention, suitable isocyanates can be selected according to final use, to adhesive In terms of heat resistance has the purposes of particular/special requirement, the general isocyanates using more than 3 functions is as crosslinking agent.To heat resistance and In terms of light resistance has the purposes of particular/special requirement, it is preferred to use aliphatic isocyanates more than 3 functions are as crosslinking agent.
Blocked isocyanate used is exactly the life that isocyanates and blocking agent as described above react in the present invention Into thing, what can be enumerated for blocking agent has formyl amidoxime, hydroxyl acetamidine, ethamine oxime, the oximes such as acetoxime, methyl ethyl ketoxime, third Acid dimethyl, diethyl malonate, methyl acetoacetate, acetylacetone,2,4-pentanedione isoreactivity diformazan base class and phenol, cresols etc. The amine such as the alcohols such as the lactams such as phenols, caprolactam, 2-Ethylhexyl Alcohol, 2,3- dimethyl pyrazoles.It is wherein gratifying It is the blocking agent of oximes, lactams, amine.
The dissociation temperature of blocked isocyanate is recommended between 90 DEG C~200 DEG C, wherein preferably 90~150 DEG C.It is low In the state of 90 DEG C, it is possible to can be dissociated during the solvent seasoning of adhesive and be destroyed cohesive, and exceeded At 200 DEG C, rotten worry occurs for the plastic sheeting for having lamination again.
In the present invention can and with of more than two kinds, more than difunctionality isocyanate compound and/or enclosed type isocyanic acid Ester.In the case of isocyanates and blocked isocyanate are used at the same time, the amount of blocked isocyanate used is total for both The 20%~100% of weight, this is a big gratifying embodiment of the invention.The curing characteristics and length of adhesive can be taken into account Phase stability.
Filler in the coating is a kind of and two or more in titanium dioxide, graphite, carbon black, barium sulfate, silica Combination.
The second feature of the coating of the present inventionIt is using above-mentioned fluorocarbon resin as component A, (is titanium dioxide by above-mentioned filler A kind of and two or more combination in titanium, graphite, carbon black, barium sulfate, silica) D components are used as, and A/D (weight ratio) is 80/ 5~30/60, preferable scope is 80/10~30/30;If higher than 80/5, the laminate of coating and Kapton does not have The effect of barrier ultraviolet completely;If less than 30/60, the adherence of coating and base material is not good enough.
If illustrating titanium dioxide used in the present invention, it is divided into rutile-type and anatase titanium dioxide, rutile-type is compared with sharp Titanium-type, because its elementary cell is made up of two titania molecules and anatase titanium dioxide is to be made up of four titania molecules, Therefore its elementary cell is smaller and close, so with larger stability and relative density, therefore with higher refractive index and Dielectric constant and relatively low heat conductivity.It is rutile titanium dioxide so currently preferred, and the preferable model of particle diameter Enclose is between 0.1~2um.More preferably between 0.2~1um.The R900 of described titanium dioxide such as E.I.Du Pont Company, R960, R101, R103, R706 etc.;The R405 of Sha Harry our company, R420, RD3 etc.;Japanese stone originates in the CR-50, CR- of industry 57, CR-super70 etc..
Preferably, graphite or/and carbon black used in the present invention, refer to by oxidation-treated graphite or/and carbon black, Dispersiveness with relatively excellent insulating properties and in the polymer.The Special black of the carbon black such as Orion companies 4,4A, 5,6 40 etc., the Emperor1200 of Cabot Co., Ltd, Emperor1600 etc..
Preferably, the nano level barium sulfate refered in particular to of barium sulfate used in the present invention, particle diameter distribution D50 < 0.8um, Preferably D50 < 0.5um.Packing material size is distributed D50 > 0.8um, shielding and anti-ultraviolet effect for coating It is not good enough.
Preferably, silica spy used in the present invention refers to dioxy made of the vapour deposition process of undefined structure SiClx, and pass through organic surface treatment, there is superior dispersibility and thickening power.The silicon dioxide compound such as Degussa ACEMATT HK400, ACEMATT HK450, ACEMATT HK460, ACEMATT OK412, ACEMATT OK500, ACEMATT OK520, ACEMATT OK607, ACEMATT OK412LC and Deng, the C803 of Grace, C805, C807, C809, C7000, CP4-8991 etc..
The 3rd feature of coating of the present invention be, the thickness range of coating is 1~20um, can not if thickness is less than 1um So that ultraviolet (280~400nm) the rejection rate > 90% of coating, as thickness is more than 20um, then coating can occur certain anti- Stickiness, and without economic benefit.Preferable range of coat thicknesses is 1~15um.
Preferably, the composition of raw materials of the coating further comprises 0.01~2% hydroxyl fluorocarbon resin curing accelerator and 0.1~2% dispersant.Curing accelerator can select tertiary amine catalyst (including its quaternary ammonium salt) and organo-metallic compound Middle one or more of combination.The dispersant can be polyvalent carboxylic acid's class dispersant, silane coupler class dispersant, silicate One or more of combinations in class dispersant, silicon dioxide compound etc..
First feature of epoxy adhesive oxidant layer of the present invention be, the addition of thermoplastic resin and/or synthetic rubber is 10~50%, if less than 10%, glue-line does not have the effect of toughness reinforcing for the Efficient Adhesive Promotion unobvious of film and metallic plate yet Fruit, glue-line are partially hard on the whole;If addition is higher than 50%, the glass transition temperature decline of glue-line is more, influences glue-line Heat resistance.
If epoxy resin used in the present invention is illustrated as bisphenol A-type, bisphenol S type, bisphenol-f type, epoxy novolac, connection The combination of one or both of benzene-type, phenol type and their hydride, aliphatic epoxy.The epoxy molecule In there is 2 epoxide groups or 3 and above epoxide group compound do not limit herein, by organosilicon, end carboxyl fourth Nitrile rubber (CTBN), acrylic acid, polyurethane, polyamide modified epoxy resin also can, on epoxy molecule segment containing resistance The bromo element of combustion, P elements, elemental sulphur, nitrogen also may be used.
Resin containing 2 epoxy-functionals on strand is such as by bisphenol A-type, bisphenol-f type, bisphenol S, talan type ring Oxygen tree fat, alicyclic type epoxy resin, biphenyl type epoxy resin.Non-brominated epoxy resin, it is commercially available as JER828, JER871, JER1001 (Mitsubishi chemistry), ELA115, ELA127 of Sumitomo Chemical, the NC-3000H etc. of Japanese chemical drug, brominated Oxygen tree fat such as jER5050, jER5048, jER5046 (Mitsubishi chemistry).
Resin such as phenol type epoxy, orthoresol type ring oxygen, N, N containing 3 epoxy-functionals on strand, N', N'- tetra- It is glycidyl -4,4'- MDA, commercially available such as the NPPA-431A70 in Taiwan South Asia, NPPN631, NPPN638.Day The EOCN-1020 of this chemical drug, XD-1000, NC-2000, NC-3000, EPPN-500.
There is the epoxy resin of 2 epoxide groups in molecular weight, the effect in flexibility and adhesive strength of the resin after solidification Preferably;Have the epoxy resin of 3 and more than 3 epoxide groups in molecular weight, the resin after solidification for lifting heat resistance with It is and effective above glass transition temperature.Summary feature, epoxy resin used in the present invention can be one of which, Either two or more is mixed.
Preferably, the thermoplastic resin can use various thermoplastic resins on the market, applicable thermoplastic resin Fat has polyester resin, acrylic resin, phenoxy resin and polyamide-imide resin.It is selectable to have phenoxy resin PPO*MX-90 (SABICINNOVATIVE PLASTICS), PKHA, PKHB, PKHB+, the PKHC of Inchem Corp. companies, PKHH, the 1256 of Mitsubishi chemical company, 4250,4275 etc.;Polyamide-imide resin Nippon Kayaku Co., Ltd. the Kayaflex series and the acrylic resin containing epoxy radicals such as Hitachi Chemical Co., Ltd .KS of company Series.
Preferably, the synthetic rubber is the mixture of one or both of acrylic rubber, nitrile rubber.Rubber It is between -50~-10 DEG C that glass, which changes transformetion range,.The ethylene acrylate rubber of acrylic rubber such as E.I.Du Pont CompanySeries, such asVMX4017, VMX5015V etc., butyronitrile Rubber for example Japanese JSRJSR-XER32, JSR-XER91 etc., Taiwan Nandi Chemical Industry Co LtdSystem Row, such as 1072,1072CG, 3245C etc..
Second feature of adhesive phase of the present invention be, the usage amount of second curing agent is 0.1~10%, if low Not high in the degree of cross linking of 0.1% glue-line, heat resistance is bad;If higher than 10%, the degree of cross linking is too high, and it is partially hard to show as glue-line, Influence cohesive force.
Use of the present invention to the second curing agent does not have special limitation requirement, any to be typically used as epoxy curing agent Material can use, be preferably based on the curing agent of polyamines and the curing agent based on acid anhydrides.Wherein, the curing agent based on polyamines What can be selected has the m-phenylene diamine (MPD), methanediamine of isophthalic two, diaminodiphenylsulfone, phenylenediamine, diaminodiphenyl-methane, double Cyanamide, polyamide curing agent.What the curing agent based on acid anhydrides can be selected has phthalic anhydride, pyromellitic dianhydride, hexahydro adjacent Phthalate anhydride etc..Above-mentioned each curing agent can be used alone, can also combination of two or more use.
The described adhesive layer of the present invention can also do following improvement:Curing agent accelerator 0.01-1% is added, to accelerate ring Reaction between oxygen tree fat and the second curing agent.Curing agent accelerator of the present invention can use of the prior art existing Curing agent accelerator, wherein it is preferred that one kind in imidazolium compounds, three organic phosphine compounds, quaternary ammonium salt and borofluoride etc. or Two or more mixing.Described imidazolium compounds preferably uses 2-methylimidazole, 1- methylimidazoles, 2- ethyl -4- methyl miaows Azoles, 2-ethyl-4-methylimidazole (2E4MZ), 1- cyanoethyls -2-ethyl-4-methylimidazole (2E4MZ-CN), 2- undecyl miaows Azoles (C11Z), 1- cyanoethyl -2- undecyl imidazoles (C11Z-CN) and 2- heptadecyl imidazoles (C17Z), each imidazoles of the above Compound can be used alone or two or more be used in mixed way.Three described organic phosphine compounds preferably use Triphenylphosphine or tributylphosphine etc..Described quaternary ammonium salt preferably uses the three of 2,4,6- tri- (dimethylamino methyl) phenol (diethacetic acid) salt or 2, three oleates of 4,6- tri- (dimethylamino methyl) phenol etc..Described borofluoride is optional With the complex compound of the complex compound of boron trifluoride and mono aminoethane, the complex compound of boron trifluoride and n-butylamine, boron trifluoride and benzylamine with And mixture more than one or both of complex compound of boron trifluoride and dimethylaniline etc..
The 3rd feature of adhesive of the present invention be, the addition of the fire retardant is 10~70%, if less than 10% Then the fire resistance of adhesive tape does not reach V-2 grades, and the bond properties of glue-line can be influenceed if higher than 70%, and is not easy in glue Disperse in water, influence Painting effect.Preferably 20~60%.
Preferably, the fire retardant is bromine (Br) flame retardant, chlorine (Cl) flame retardant, phosphorus (P) flame retardant, nitrogen (N) Flame retardant, silicon (Si) flame retardant, metal oxyhydroxide based flame retardant, metal oxide fire retardant, metal boride resistance Fire one or more of mixing in agent etc..Wherein it is preferred that phosphorus (P) flame retardant, nitrogen (N) flame retardant, the resistance of silicon (Si) system Fire the one or more in agent, metal oxyhydroxide based flame retardant, metal oxide fire retardant, metal boride fire retardant etc. Mixing.
If illustrating phosphonium flame retardant used in the present invention can select to use organic phosphorus compound, such as phenolic group Alamos Oligomer (FP110) etc.;Organophosphonate, condensation polymer type non-halogen phosphoric acid ester, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate (two Toluene) ester, butylbenzene system phosphate, propyl benzene system phosphate, phenoxy group polyphosphazene, dimethyl methyl phosphonate, diethyl ethylphosphate, P isopropylbenzoic acid base phenylester, the base ester of phosphoric acid tert-butyl benzene two, four aryl arlydene biphosphonates, resorcin phosphate, four benzene Base bisphenol-A-bisphosphate, pentaerythrite melamine phosphate etc.;And phosphinate, such as the phosphinate of alkali metal: Phosphonous acid sodium or phosphonous acid potassium, polyphosphoric acids ammonium salt, aluminum diethylphosphinate, diethyl phosphinic acids zinc etc..
If illustrate nitrogenous resistance of the nitrogen combustion inhibitor selection nitrogen content used in the present invention in the range of 15-30 mass % Fire agent, preferably nitrogenous flame ratardant of the nitrogen content in the range of 15-25 mass %.Preferably nitrogenous polyphosphate chemical combination of the invention Thing, such as:Melamine polyphosphate (MPP), polyphosphoric acids ammonium salt, melamine, melamine phosphate, melamine cyanogen Uric acid complex compound, piperazine polyphosphate or their mixture.Specific example has melamine pyrophosphate, melamine three Phosphate, melamine pentaphosphate, piperazine pyrophosphate, piperazine triphosphate and piperazine pentaphosphate.
If it can be inorganic silicon dioxide based flame retardant or organosilicon to illustrate silicon-series five-retardant used in the present invention Based flame retardant, the inorganic silicon dioxide based flame retardant include white carbon, wollastonite, mica, kaolin, montmorillonite and talcum powder Deng;The silicone based flame retardant changes including organosiloxane class, organosilicon epoxy resin, silicon rubber and caged silsesquioxane Property polymer etc..
The metal oxyhydroxide based flame retardant includes aluminium hydroxide or magnesium hydroxide etc..
The metal oxide includes antimony oxide, antimony oxide, iron oxide, tin oxide etc..
The metal boride fire retardant has Firebrake ZB, barium borate etc..
Appropriate dispersant 0.01-2% can also be added in the adhesive phase of the present invention, is advantageous to lift fire-retardant filler and tree Compatibility between fat, the dispersant can be polyvalent carboxylic acid's class dispersant, coupling agent class dispersant, silicates dispersant, One or more of combinations in silicon dioxide compound etc..Preferably titanate coupling agent, aluminate coupling agent, organosilicon One or more of combinations in alkane coupling agent, Organic Chromium complex coupling agent, boric acid ester coupler, silicon dioxide compound, The coupling agent class dispersant is more preferably one kind in titanate coupling agent, aluminate coupling agent, organo silane coupling agent Or several combination.
The titanate coupling agent such as isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, (dioctyl of isopropyl three Phosphoric acid acyloxy) titanate esters, the oleic acid acyloxy of isopropyl two (dioctyl phosphoric acid acyloxy) titanate esters, monoalkoxy unsaturated lipid Fat acid titanate esters, the chelate of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine, double (two octyloxy Jiao's phosphorus Perester radical) ethylene titanate esters etc..
The aluminate coupling agent is if any aluminium titanium compound, two (ethyl acetoacetate base) aluminic acid isopropyl esters, two (levulinics Ketone) aluminic acid diisopropyl ester, isopropyl stearic acid oxygen base aluminum acid ester, isopropyl stearic acid oxygen base aluminum acid ester etc..
The organo silane coupling agent for example amino silane, epoxy silane, methacryloxypropyl silane, vinyl silanes, Alkyl silane, sulfuric silane, phenoxy group silane, isocyanatosilanes, silicon fluoride etc..
The present invention can also add appropriate antioxidant, its addition 0.01-3%.Described antioxidant is preferably using more First hindered phenol type antioxidant, such as antioxidant lrganox1010 (four【3- (3,5- di-t-butyl -4- hydroxyphenyls) propionic acid】Season amylalcohol Ester), phosphite antioxidant 168 or phosphite antioxidant 626 etc. or their mixture.
According to a preferred aspect of the present invention:The composition of raw materials of described adhesive layer includes following components:
The present invention also provides a kind of photovoltaic module busbar, including the first insulating tape, the metal level being cascading With the second insulating tape, first insulating tape and/or the second insulating tape are above-mentioned insulating tape, the insulating tape Described adhesive layer bonds with the metal level.
The present invention also provides a kind of photovoltaic module, and its busbar used includes above-mentioned photovoltaic module busbar.
Because above-mentioned technical proposal is used, cost is lower compared with prior art by the present invention.
The coating of the present invention has excellent adherence with polyimides, is still protected even in drawing Gree after hot and humid 0~1 grade is held, the UV separation of coating is outstanding.
The adhesive phase of insulating tape of the present invention adds certain content by using the specific epoxy resin of certain content Thermoplastic resin and/or synthetic rubber and curing agent and fire retardant so that prepare adhesive phase not only with insulated base material layer With excellent adherence, also there is excellent cohesive with metal.
The insulating tape of the present invention has the performance of the environmental aging such as uvioresistant, heat shock resistance, thermal shock, damp and hot. By the insulating tape hot pressing of the present invention on metallic plate or metal bus bars, the insulation available for photovoltaic module busbar.
Embodiment
The preferred embodiment of the invention is described in detail below in conjunction with specific embodiment.
1、The preparation of insulating tape
It is 50% to be dissolved in butyl acetate (or for conventional ethyl acetate, third by mass percentage by hydroxyl fluorocarbon resin Ketone, toluene, dimethylbenzene, DMF etc.) in solvent, addition hydrogenated epoxy resin, carbon black filler, dispersant BYK9076, by scattered and sanded treatment.Again plus isocyanate curing agent, dibutyl tin laurate curing accelerator, and Even stirring, the coating of 5 μ m-thicks is evenly coated with Kapton (PI), will be molten with 150 DEG C/5m ins programming rate Agent heating evaporation is done, and is then wound standby.
It (or is normal that epoxy resin, thermoplastic resin and/or synthetic rubber are dissolved in into butanone for 20% by mass percentage Acetone, toluene) it is 20% to be dissolved in butanone (or for conventional acetone, toluene, dimethylbenzene, N, N- bis- by mass percentage NMF etc.) in solvent, fire retardant is then added in resin solution, by scattered and sanded treatment.Again plus second is solid Agent, curing accelerator and uniform stirring.In being simultaneously evenly coated with addition for above-mentioned cated Kapton (PI) The adhesive of 25 μ m-thicks, solvent heating evaporation is done with 100 DEG C/5m ins programming rate, compound mould release membrance or release liners, so After wind, be made insulating tape.
After coating, carrying out surface treatment effect to Kapton in advance can be more preferable for above coating and adhesive, Such as sided corona treatment, plasma treatment.
2nd, the preparation of busbar
On the PI insulating tapes after completing to be coated with, flat tin-coated copper strip (glue surface is to tin-coated copper strip), Ran Hou are placed Symmetrical another PI insulating tape (glue surface is to tin-coated copper strip) is placed on copper strips again, by 180 DEG C/0.2Mpa/2~3S of high temperature Rolling be made photovoltaic Bus bar (busbar), then be crosslinked by solidification in 80~160 DEG C × 1~2 hour.
Prepare embodiment, the adhesive phase and composition of raw materials and insulating tape and manufactured photovoltaic module busbar of comparative example Performance as shown in Tables 1 and 2, the dosage of each component in Tables 1 and 2 is in parts by weight.
Table 1 is the composition of raw materials and insulating tape and manufactured photovoltaic group of the adhesive phase of insulating tape in embodiment 1-6 The Evaluation results of part busbar
Table 2 is the composition of raw materials and insulating tape and manufactured photovoltaic group of the adhesive phase of insulating tape in comparative example 1-7 The Evaluation results of part busbar
The evaluation result of Tables 1 and 2 includes insulating tape and the photovoltaic conflux bar (bus-bar) made with insulating tape Some performance evaluations.Raw material in Tables 1 and 2:
Raw material in Tables 1 and 2:
GK570:Fluorocarbon resin, Daikin fluorination work Industrial Co., Ltd
TPA100:Polyisocyanate curing agent, Asahi Kasei Corporation
Special black4:Carbon black, German Ou Li are grand
BYK-9076:Dispersant, German Bi Ke
EP4080E:Hydrogenated bisphenol A epoxy resin, Ai Dike Co., Ltd.
DBTDL:Dibutyl tin laurate
JER-828:Bisphenol A type epoxy resin, Mitsubishi chemistry
XD-1000:Poly- [(phenyl glycidyl ether)-CO- bicyclopentadiene], Nippon Kayaku K. K
XER-32:Nitrile rubber (NBR), Japanese JSR Corp.
Acrylic rubber, du pont company
PX200:Condensation polymer type non-halogen phosphoric acid ester, it is big eight chemistry of Japan;
MC6000:Melamine cyanurate, Nissan Chemical;
DICY:Dicyandiamide, Ningxia Jia Feng Chemical Co., Ltd.s
3rd, comprehensive performance evaluation result
◎:Represent that combination property is optimal;○:Performance OK is represented, requirement can be met;
△:Represent poor performance;×:Represent performance extreme difference.
4th, the method for above-mentioned assessment item
(1) thickness
Gone to measure the thickness of coating and adhesive phase with tenthousandth micrometer.
(2) coating draws Gree
Adherence between coating and insulating barrier, with 3M adhesive tapes, reference GB/T 9286-1998 standard, adherence grade Divided according to 0~5 grade.
(3) light rejection rate (280~1100nm)
Tested using Japanese Shimadzu UV-3600 types spectrophotometer.
(4) adhesion strength
Insulating tape presses with tin-coated copper strip by 150~180 DEG C/0.5~2Mpa/0.5 of high temperature~2hrs, then by 80 Solidification crosslinking in~160 DEG C × 1~2 hour.Recover to 25 DEG C, 20 minutes of room temperature, test between insulating tape and tin-coated copper strip Adhesive strength, unit N/5mm, establishing criteria, 180 ° of angle measurements, peeling rate 100mm/min.
(5) heat shock resistance
On PI insulating tapes after coating, flat tin-coated copper strip (glue surface is to tin-coated copper strip) is placed, then on copper strips Symmetrical another PI insulating tape (glue surface is to tin-coated copper strip) is placed again, by 150~180 DEG C/0.5~2Mpa/0.5 of high temperature ~2hrs is pressed, then is crosslinked by solidification in 80~160 DEG C × 1~2 hour.Photovoltaic Bus bar (busbar), edge envelope is made Side about 3mm.It is positioned over this manufactured busbar under 200 DEG C of environment and stops 10s, is then recovered to room temperature, observe insulating tape It is bad that gassing, layering, contraction etc. are whether there is between insulating tape and insulating tape and tin-coated copper strip.Outward appearance is unchanged It is then OK, otherwise NG.
(6) cold-resistant thermal circulation performance
Sample sample preparation is same as above, and sample is positioned in cold cycling case, -40~105 DEG C/200 times circulations, -40 DEG C/constant temperature 1H, -40 DEG C rise to 105 DEG C/0.5H, and 105 DEG C/constant temperature 1H, 105 DEG C are down to -40 DEG C/0.5H, and the above is circulation in 3 hours. Observed after cold cycling whether there is between insulating tape and insulating tape and insulating tape and tin-coated copper strip gassing, layering, Contraction etc. is bad.Unchanged outward appearance is then OK, otherwise NG.
(7) wet and heat ageing resistant
Sample sample preparation is same as above, and sample is positioned in hot and humid environment case, 85 DEG C × 85%RH × 1000H, hydrothermal aging Afterwards between insulating tape and insulating tape, and bubble-free, delamination, contraction between insulating tape and tin-coated copper strip, outward appearance is without change Change is then OK, otherwise NG.
(8) anti-flammability
Insulating tape after being coated with, according to the long 125mm of size × wide 13mm sample preparations, according to the standards of UL 94, fired Burn.And establishing criteria judges flame retardant rating.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, it should all be included within the scope of the present invention.

Claims (10)

1. a kind of insulating tape, it is characterised in that including insulated base material layer, the coating formed on the insulating substrate is laminated And form the adhesive phase on the another side of the insulated base material layer;
Based on weight/mass percentage composition, the composition of raw materials of described coating includes following component:
The fluorocarbon resin 30 ~ 80% of hydroxyl or amino;
Filler 5 ~ 60%;
Auxiliary agent 0.1 ~ 10%;
First curing agent 1 ~ 25%;
First curing agent is one or more kinds of in Isocyanates curing agent, amino resins, acid anhydride type curing agent Combination;
Based on weight/mass percentage composition, the composition of raw materials of described adhesive layer includes following components:
Epoxy resin 20 ~ 60%;
Thermoplastic resin and/or synthetic rubber 5 ~ 50%;
Second curing agent 0.1 ~ 10%;
Fire retardant 10 ~ 70%.
2. insulating tape according to claim 1, it is characterised in that:Described auxiliary agent is epoxide, the Asia of carbonization two The mixture of one or both of amines so that coating adhesive force after wet-heat resisting can be intersected real by hundred lattice Test and reach 0 ~ 1 grade of level.
3. insulating tape according to claim 1, it is characterised in that:The fluorocarbon resin of the hydroxyl be tetrafluoroethene/ The copolymer of vinyl ethers, copolymer, CTFE and the vinyl ester copolymer of tetrafluoroethylene/ethylene base ether monomer, three Composition more than one or both of fluorine vinyl chloride and vinyl ether co-polymer, Kynoar.
4. insulating tape according to claim 1, it is characterised in that:The filler is titanium dioxide, nanoscale graphite, charcoal One or more kinds of combination in black, barium sulfate, silica.
5. insulating tape according to claim 1, it is characterised in that:The composition of raw materials of the coating further comprises 0.01 ~ The curing accelerator and 0.1 ~ 2% dispersant of 2% hydroxyl fluorocarbon resin.
6. insulating tape according to claim 1, it is characterised in that:The epoxy resin is bisphenol A-type, bisphenol S type, double The combination of one or both of phenol F types, epoxy novolac, biphenyl type, phenol type and their hydride, aliphatic epoxy.
7. insulating tape according to claim 1, it is characterised in that:The thermoplastic resin is polyester resin, acrylic acid Combination more than one or both of resinoid, phenoxy resin and polyamide-imide resin;The synthetic rubber is third The combination of one or both of olefin(e) acid rubber, nitrile rubber containing end carboxyl.
8. insulating tape according to claim 1, it is characterised in that:Second curing agent uses the solidification based on polyamines Agent and/or the curing agent based on acid anhydrides, consolidating for 0.01 ~ 2% epoxy resin is further comprises in the composition of raw materials of described adhesive layer Change accelerator.
9. a kind of photovoltaic module busbar, including the first insulating tape, metal level and the second insulating tape being cascading, It is characterized in that:First insulating tape and/or the second insulating tape are described in any one of claim 1 ~ 8 claim Insulating tape, the described adhesive layer of the insulating tape bonds with the metal level.
10. a kind of photovoltaic module, its busbar used includes the photovoltaic module busbar described in claim 9.
CN201710950891.0A 2017-10-13 2017-10-13 Photovoltaic module busbar insulating tape, busbar and photovoltaic module containing same Active CN107629713B (en)

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WO2019072016A1 (en) * 2017-10-13 2019-04-18 苏州赛伍应用技术股份有限公司 Photovoltaic assembly bus-bar insulating tape, bus-bar containing same, and photovoltaic assembly
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CN111234734A (en) * 2020-02-27 2020-06-05 招远春鹏电子科技有限公司 Environment-friendly glue solution for flexible copper-clad plate and preparation method thereof
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CN115386314A (en) * 2022-09-01 2022-11-25 苏州福斯特光伏材料有限公司 A film for photovoltaic backplate is repaired
CN115386314B (en) * 2022-09-01 2024-01-05 苏州福斯特光伏材料有限公司 Film for repairing photovoltaic backboard

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