CN109666445B - Resin composition, insulating glue film containing resin composition for laminated busbar and preparation method of insulating glue film - Google Patents
Resin composition, insulating glue film containing resin composition for laminated busbar and preparation method of insulating glue film Download PDFInfo
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- CN109666445B CN109666445B CN201811613845.2A CN201811613845A CN109666445B CN 109666445 B CN109666445 B CN 109666445B CN 201811613845 A CN201811613845 A CN 201811613845A CN 109666445 B CN109666445 B CN 109666445B
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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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
- H01B7/0208—Cables with several layers of insulating material
- H01B7/0216—Two layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
- H01B7/0291—Disposition of insulation comprising two or more layers of insulation having different electrical properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a resin composition, an insulating glue film for a laminated busbar containing the resin composition and a preparation method of the insulating glue film. The resin composition disclosed by the invention is excellent in high-temperature resistance, the flame retardance of the insulating adhesive film for the laminated busbar prepared by using the resin composition can reach UL941VTM-0 level, the laminating temperature is low, the bonding performance is good, and meanwhile, the resin composition has good high-low temperature peel strength, dimensional stability, processability and reliability, and can meet the performance requirement of the high-reliability laminated busbar with the working temperature of 130 ℃.
Description
Technical Field
The invention belongs to the technical field of insulating glue films for laminated busbars, and relates to a resin composition, an insulating glue film for laminated busbars containing the resin composition and a preparation method of the resin composition.
Background
The laminated Busbar is also called a composite Busbar, a laminated Busbar, a composite copper bar, a low-inductance Busbar and the like, and the English name of the laminated Busbar is called Laminatd Busbar. The laminated busbar is used as a connecting bar with a multi-layer composite structure and can be used as a highway of a power distribution system. Compared with the traditional complex, heavy, time-consuming and labor-consuming wiring method, the laminated busbar can provide a power distribution system with high technical content and a clear structure which is easy to design. The high-power module has the characteristics of repeatable electrical performance, low inductance impedance, strong anti-interference capability, high reliability and the like, and therefore, the high-power module can be used as an electrical connecting component of high-power modules. In addition, the laminated busbar has the characteristics of simple assembly, compact structure and the like, and is widely applied to conversion power modules of wind power, photovoltaic and electric traction equipment, large-scale network equipment and the like.
With the increasing working temperature, the high-reliability laminated busbar with the working temperature of 130 ℃ is replacing the laminated busbar with the working temperature of 105 ℃, and the high-reliability laminated busbar also puts higher requirements on the temperature resistance and the reliability of materials. The laminated busbar is mainly composed of a conductor material and an insulating material; the conductor material is mainly the tinned copper busbar, and its temperature resistance generally does not have the problem, and from this, insulating material's temperature resistance and reliability become a bottleneck that promotes the female operating temperature of arranging of stromatolite.
CN 106700509A discloses a halogen-free thermoplastic resin composition, which comprises, by mass, 40-80 parts of copolyamide resin, 5-35 parts of saturated polyester resin, 1-10 parts of compatilizer, 10-150 parts of halogen-free flame retardant and 0.1-1 part of antioxidant. The halogen-free thermoplastic resin composition obtained by taking the saturated polyester resin and the copolyamide resin as the main resin is halogen-free, environment-friendly, free of curing agent, good in high-temperature fluidity, capable of meeting the low-temperature pressing requirement, and capable of being used as the adhesive for the laminated busbar, but the prepared insulating adhesive film for the laminated busbar can only meet the application requirement of 105 ℃.
Therefore, finding a high-temperature-resistant resin composition with excellent comprehensive performance to be applied to a 130 ℃ high-reliability laminated busbar becomes an urgent problem to be solved in the industry.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a resin composition, an insulating glue film for a laminated busbar containing the resin composition and a preparation method of the insulating glue film.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a resin composition comprising a copolyamide resin, a phenolic resin, a phenoxy resin, a curing agent and a flame retardant dispersed in an organic solvent.
The copolyamide resin has strong polarity, good heat resistance, good metal bonding performance, poor polymer film bonding performance and insufficient aging resistance. According to the invention, the phenolic resin and the phenolic resin are introduced into the copolyamide resin, the number of groups which can react in the composition is increased through the cooperation of the copolyamide resin, the phenolic resin and the phenolic resin, the composition has high crosslinking density, the heat resistance and the chemical resistance are improved, meanwhile, the defects of the adhesive property of the copolyamide can be improved through a large amount of hydroxyl groups contained in the phenolic resin and the phenolic resin, the residual carbon rate of the phenolic resin is high, the flame retardant property is excellent, the using amount of the additive phosphorus-containing flame retardant can be reduced, and the negative effects in the aspects of hygroscopicity, the adhesive property, the insulativity and the like caused by the large amount of the additive phosphorus-containing flame retardant are avoided. The resin composition has excellent heat resistance, heat aging resistance, flame retardance and adhesiveness, and meets the application requirement of the laminated busbar with the working temperature of 130 ℃.
Preferably, the content of each component in the resin composition is as follows: 40 to 50 parts by weight (e.g., 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, or 50 parts by weight) of a copolyamide resin, 10 to 20 parts by weight (e.g., 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight) of a phenolic resin, 20 to 30 parts by weight (e.g., 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, or 30 parts by weight) of a phenoxy resin, 5 to 10 parts by weight (e.g., 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight) of a curing agent, and 5 to 10 parts by weight (e.g., 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight.
Preferably, the solid content of the resin composition is 30 wt% to 60 wt%, such as 30 wt%, 33 wt%, 35 wt%, 38 wt%, 40 wt%, 43 wt%, 45 wt%, 48 wt%, 50 wt%, 55 wt%, 58 wt% or 60 wt%. Within the range of solid content, the proper viscosity can be obtained, good processability is provided, and apparent defects are avoided in the coating process.
Preferably, the copolyamide resin is obtained by polycondensation of dibasic acid and diamine.
Preferably, the molar ratio of the diacid to the diamine is 1:1.05 to 1.1, such as 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09, or 1: 1.1. Controlling the mole ratio of the dibasic acid to the diamine can control the copolyamide resin to have an appropriate amine value and molecular weight.
Preferably, the copolyamide resin has an amine value of 7-15mgKOH/g, for example 7mgKOH/g, 7.5mgKOH/g, 8mgKOH/g, 8.5mgKOH/g, 9mgKOH/g, 9.5mgKOH/g, 10mgKOH/g, 11mgKOH/g, 12mgKOH/g, 13mgKOH/g, 14mgKOH/g or 15 mgKOH/g. If the amine value is too low, the crosslinking density is insufficient, which affects the heat resistance; if the amine value is too high, the reaction speed is too fast, which affects the storage life of the adhesive film and easily causes the adhesive film to become brittle.
Preferably, the dibasic acid comprises 50 mol% or more of a non-aromatic dibasic acid and less than 50 mol% of an aromatic dibasic acid; the diamine contains more than 80 mol% of non-aromatic diamine and less than 20 mol% of aromatic diamine. The control of the composition of the dibasic acid and the composition of the diamine is beneficial to controlling the copolyamide resin to have proper glass transition temperature and crystallinity.
Preferably, the copolyamide resin has a glass transition temperature of 10-40 ℃, for example 10 ℃, 13 ℃, 15 ℃, 18 ℃, 20 ℃, 25 ℃, 28 ℃, 30 ℃, 35 ℃, 38 ℃ or 40 ℃. If the glass transition temperature is too low, the surface of the adhesive film is easily sticky, and the operability and heat resistance are affected; when the glass transition temperature is too high, the flexibility of the adhesive film becomes insufficient, and the processability is impaired.
Preferably, the copolyamide resin has a crystallinity of 10% to 18%, for example 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% or 18%, and if the crystallinity is too high, it cannot be dissolved by a solvent, which affects processability, and if the crystallinity is too low, heat resistance is insufficient.
Preferably, the non-aromatic dibasic acid comprises one of succinic acid, adipic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid or a combination of at least two thereof.
Preferably, the aromatic dibasic acid comprises one or a combination of at least two of terephthalic acid, phthalic acid and isophthalic acid.
Preferably, the non-aromatic diamine comprises one or a combination of at least two of ethylenediamine, bis (3-methyl-4-aminocyclohexyl) methane (MACM), p-bis (aminocyclohexyl) methane (PACM).
Preferably, the aromatic diamine includes one or a combination of at least two of p-phenylenediamine (PPDA), 4 '-diaminodiphenyl ether (ODA), 2' -bis [4- (4-aminophenoxy) phenyl ] propane (BAPP).
Preferably, the number average molecular weight of the copolyamide resin is 8000-12000, such as 8000, 8300, 8500, 9000, 9500, 10000, 11000 or 12000, and if the molecular weight is too high, the dissolution is difficult, and the viscosity after the dissolution is too large, which affects the coating appearance; if the molecular weight is too low, the cohesive strength is insufficient and the compatibility is poor.
In the present invention, the copolyamide is prepared as follows: introducing nitrogen into a high-pressure reaction kettle with a stirrer, a condenser pipe and a thermometer, then adding dibasic acid and diamine, starting stirring, heating to the temperature of 240-280 ℃, reacting at constant temperature for 2 hours, then releasing to normal pressure, and stopping stirring to obtain the copolyamide resin.
Preferably, the phenolic resin is linear phenolic resin which has good storage stability and can prolong the storage life of the adhesive film.
Preferably, the phenolic resin is any one of bisphenol a type phenolic resin, o-cresol formaldehyde resin, phenol phenolic resin, aralkyl phenolic resin, novolac type phenolic resin or phenolic resin containing triazine structure or a mixture of at least two of the above.
Preferably, the phenoxy resin has the following structural formula:
wherein R is1、R2、R3、R4represents-H, -Br or a P-containing group, R1、R2、R3、R4Represent the same or different groups; n represents an integer from 50 to 150, such as 50, 55, 60, 65, 70, 80, 90, 100, 110, 120, 130, 140, 145, 148 or 150, etc.
Preferably, the curing agent is one or two of a blocked isocyanate curing agent and an anhydride curing agent.
Preferably, the deblocking temperature of the blocked isocyanate curing agent is 80 ℃ to 160 ℃, such as 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃. Preferably, the blocked isocyanate curing agent releases small molecules when unblocked at a high temperature to form micro bubbles in a glue layer, thereby causing deterioration in insulation properties, heat resistance and adhesive properties.
In the present invention, the blocked isocyanate curing agents are commercially available as TAKENATE XB-G282, TAKENATE B-820NP from Mitsui Chemicals; desmodur BL3175SN, Desmodur BL3370MPA, etc. of Bayer materials technology.
Preferably, the anhydride curing agent is any one of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and pyromellitic dianhydride or a combination of at least two of the tetrahydrophthalic anhydride, the hexahydrophthalic anhydride, the methyl hexahydrophthalic anhydride and the pyromellitic dianhydride.
Preferably, the flame retardant is a phosphorus-containing flame retardant.
In the invention, the flame retardant used for preparing the insulating adhesive film for the laminated busbar needs to consider the influence of the flame retardant on the performances such as high and low-temperature peel strength, wet and heat aging resistance, cold and heat shock resistance, processability and the like besides the flame retardant efficiency.
Preferably, the phosphorus-containing flame retardant is SPB-100 produced by Otsuka type chemical Co., Ltd; OP-930, OP-935 manufactured by Germany Kelain; SP-703H manufactured by four chemical industries, Ltd., and the like, and the phosphorus-containing flame retardant may be any one of these flame retardants or a combination of at least two of these flame retardants.
Preferably, the organic solvent is one or a combination of at least two of ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, cyclohexanol, isoamyl alcohol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, butanone, acetone, cyclohexanone, toluene, xylene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or ethyl acetate.
In another aspect, the invention provides an insulating adhesive film for a laminated busbar, which includes an insulating film and the resin composition coated on the insulating film.
Preferably, the insulating film is any one of a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polyethylene naphthalate (PEN) film, a Polyimide (PI) film, or a polyisophthaloyl metaphenylene diamine (NOMEX) film.
Preferably, the insulating film has a thickness of 100 to 250 μm (e.g., 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, 200 μm, 220 μm, 240 μm, or 250 μm), and the resin composition coated on the insulating film has a thickness of 10 to 50 μm (e.g., 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm). If the coating thickness of the resin composition is less than 10 mu m, the adhesive layer is difficult to well infiltrate the bonded interface, and the peel strength is low; if the coating thickness is more than 50 μm, the existing coating equipment is difficult to realize, the coating appearance is poor, and the insulating adhesive film has large gumming during hot pressing, thereby influencing the processability.
The resin composition disclosed by the invention is excellent in high-temperature resistance, the flame retardance of the insulating adhesive film for the laminated busbar prepared by using the resin composition can reach UL94 VTM-0 level, the laminating temperature is low, the bonding performance is good, and meanwhile, the resin composition has good high-low temperature peel strength, dimensional stability, processability and reliability, and can meet the requirement of the laminated busbar with high reliability at the working temperature of 130 ℃.
On the other hand, the invention provides a preparation method of the insulating glue film for the laminated busbar, which comprises the following steps:
(1) dispersing copolyamide resin, phenolic resin, phenoxy resin, a curing agent and a flame retardant in an organic solvent to obtain a resin composition;
(2) and (2) coating the resin composition obtained in the step (1) on an insulating film, and drying to obtain the insulating glue film for the laminated busbar.
In the present invention, in the step (1), a dispersion liquid is obtained by dispersing the copolyamide resin, the phenolic resin, the phenoxy resin, the curing agent and the flame retardant in the organic solvent by using a ball mill, a pot mill, a sand mill or the like in combination with a high-shear stirring apparatus.
The coating of the step (2) is to coat the resin composition on the insulating film using a coating apparatus.
Preferably, the drying of step (2) is achieved by an on-line drying oven, and the drying is heating at 80 to 160 ℃ (e.g., 80 ℃, 85 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃) for 2 to 10 minutes (e.g., 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes). And in the drying process, removing the organic solvent to form a partial cross-linked resin composition layer, and rolling to obtain the insulating adhesive film for the laminated busbar.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the copolyamide resin is matched with the phenoxy resin and the phenolic resin, so that the number of groups capable of reacting in the composition is increased, the composition has higher crosslinking density, the heat resistance, the chemical resistance and the flame retardance are improved, meanwhile, a large number of hydroxyl groups in the phenolic resin and the phenoxy resin can improve the defect of the adhesive property of copolyamide, the phenolic resin has higher carbon residue rate and excellent flame retardance, the using amount of the additive phosphorus-containing flame retardant can be reduced, and the negative effects in the aspects of hygroscopicity, adhesive property, insulativity and the like caused by the large amount of the additive phosphorus-containing flame retardant are avoided. The resin composition has excellent heat resistance, heat aging resistance, flame retardance and adhesiveness, and meets the application requirement of the laminated busbar with the working temperature of 130 ℃.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation examples 1 to 4 and preparation comparative examples 1 to 4
The copolyamide resin was prepared by polycondensation of a dibasic acid and a diamine, and the selection of the raw materials and the contents thereof are shown in table 1 (the contents of the components in table 1 are in terms of molar amount).
TABLE 1
The copolyamide prepared was determined as follows:
(1) determination of the number average molecular weight of the copolyamide
The gel chromatography (GPC) was used for the measurement.
(2) Measurement of glass transition temperature of copolyamide
The temperature is increased from-20 ℃ to 150 ℃ by adopting a Differential Scanning Calorimeter (DSC) for testing, wherein the heating rate is 5K/min, and the nitrogen atmosphere is adopted.
(3) Copolyamide crystallinity determination
The X-ray diffraction test, the Ni sheet filtering, the target type Cu, the radiation Cu-Ka, the voltage 36KV, the current 25Ma, the test range 2 theta 5-50 degrees, and the scanning speed 8 DEG/min are adopted.
(4) Determination of amine number
The test was carried out by perchloric acid-glacial acetic acid nonaqueous titration.
The properties of the copolyamide obtained by measurement are shown in table 2 below.
TABLE 2
Example 1
A resin composition comprising, by weight, 40 parts of the copolyamide obtained in preparation example 1, 10 parts of bisphenol A type phenol resin, 20 parts of phenoxy resin, 5 parts of blocked isocyanate curing agent (TAKENATE XB-G282), and 10 parts of phosphorus-containing flame retardant (SPB-100).
The above components were adjusted with cyclohexanone to form a liquid dispersion (solid content: 30%) and mixed to prepare a resin composition. The resin composition is applied to an insulating glue film for a laminated busbar.
Coating the halogen-free resin composition on a PET insulating film with the thickness of 125 mu m by a coating machine, wherein the coating thickness is 30 mu m; then, the resultant was treated at 120 ℃ for 5 minutes to volatilize the solvent, thereby forming a partially cured resin composition layer on the PET insulating film to obtain an insulating adhesive film for a laminated bus bar.
Example 2
A resin composition comprises 45 parts by weight of the copolyamide obtained in preparation example 2, 15 parts by weight of an o-cresol formaldehyde resin, 25 parts by weight of a phenoxy resin, 10 parts by weight of a blocked isocyanate curing agent (TAKENATE B-820NP) and 8 parts by weight of a phosphorus-containing flame retardant (OP-930).
The above components were adjusted with ethyl acetate to form a liquid dispersion (solid content: 40%), and mixed to prepare a resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PBT insulating film with the thickness of 150 mu m by a coating machine, wherein the coating thickness is 10 mu m; and then treated at 150 ℃ for 5 minutes to volatilize the solvent, and a partially cured resin composition layer is formed on the PBT insulating film, so that the insulating adhesive film for the laminated busbar is obtained.
Example 3
A resin composition comprises 50 parts by weight of copolyamide obtained in preparation example 3, 20 parts by weight of phenolic novolac resin, 30 parts by weight of phenoxy resin, 10 parts by weight of blocked isocyanate curing agent (Desmodur BL3175SN) and 10 parts by weight of phosphorus-containing flame retardant (OP-935).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Example 4
A resin composition comprising, by weight, 48 parts of the copolyamide obtained in preparation example 4, 18 parts of a phenol aralkyl resin, 27 parts of a phenol epoxy resin, 9 parts of a blocked isocyanate curing agent (Desmodur BL3370MPA) and 5 parts of a phosphorus-containing flame retardant (SP-703H).
The components are adjusted by propylene glycol monomethyl ether acetate to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a NOMEX insulating film with the thickness of 250 μm by using a coating machine, wherein the coating thickness is 50 μm; then, the resultant was treated at 160 ℃ for 2 minutes to volatilize the solvent, thereby forming a partially cured resin composition layer on the NOMEX insulating film, thereby obtaining an insulating adhesive film for laminated busbars.
Example 5
A resin composition comprising, by weight, 40 parts of the copolyamide obtained in preparation example 1, 10 parts of a bisphenol A type phenol resin, 20 parts of a phenoxy resin, 5 parts of tetrahydrophthalic anhydride, and 10 parts of a phosphorus-containing flame retardant (SPB-100).
The above components were adjusted with cyclohexanone to form a liquid dispersion (solid content: 30%) and mixed to prepare a resin composition. The resin composition is applied to an insulating glue film for a laminated busbar.
Coating the halogen-free resin composition on a PET insulating film with the thickness of 125 mu m by a coating machine, wherein the coating thickness is 30 mu m; then, the resultant was treated at 120 ℃ for 5 minutes to volatilize the solvent, thereby forming a partially cured resin composition layer on the PET insulating film to obtain an insulating adhesive film for a laminated bus bar.
Example 6
A resin composition comprises 45 parts by weight of copolyamide obtained in preparation example 2, 15 parts by weight of o-cresol formaldehyde resin, 25 parts by weight of phenoxy resin, 10 parts by weight of hexahydrophthalic anhydride and 8 parts by weight of phosphorus-containing flame retardant (OP-930).
The above components were adjusted with ethyl acetate to form a liquid dispersion (solid content: 40%), and mixed to prepare a resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PBT insulating film with the thickness of 150 mu m by a coating machine, wherein the coating thickness is 10 mu m; and then treated at 150 ℃ for 5 minutes to volatilize the solvent, and a partially cured resin composition layer is formed on the PBT insulating film, so that the insulating adhesive film for the laminated busbar is obtained.
Example 7
A resin composition comprises 50 parts by weight of copolyamide obtained in preparation example 3, 20 parts by weight of phenolic novolac resin, 30 parts by weight of phenoxy resin, 10 parts by weight of methylhexahydrophthalic anhydride and 10 parts by weight of phosphorus-containing flame retardant (OP-935).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Example 8
A resin composition comprising, by weight, 48 parts of the copolyamide obtained in preparation example 4, 18 parts of a phenol aralkyl resin, 27 parts of a phenoxy resin, 9 parts of pyromellitic dianhydride, and 5 parts of a phosphorus-containing flame retardant (SP-703H).
The components are adjusted by propylene glycol monomethyl ether acetate to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a NOMEX insulating film with the thickness of 250 μm by using a coating machine, wherein the coating thickness is 50 μm; then, the resultant was treated at 160 ℃ for 2 minutes to volatilize the solvent, thereby forming a partially cured resin composition layer on the NOMEX insulating film, thereby obtaining an insulating adhesive film for laminated busbars.
Comparative example 1
A resin composition comprising, by weight, 30 parts of the copolyamide resin obtained in preparation example 1, 10 parts of bisphenol A type phenol resin, 20 parts of phenoxy resin, 5 parts of blocked isocyanate curing agent (TAKENATE XB-G282), and 10 parts of phosphorus-containing flame retardant (SPB-100).
And (3) adjusting the components by using cyclohexanone to form liquid dispersion liquid (the solid content is 30 percent), and mixing to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
The halogen-free resin composition was coated on a PET insulating film having a thickness of 125 μm by a coater to a coating thickness of 30 μm, followed by treatment at 120 ℃ for 5 minutes to volatilize the solvent and form a partially cured resin composition layer on the PET insulating film to obtain an insulating film for a laminated busbar.
Comparative example 2
A resin composition comprises 55 parts by weight of the copolyamide obtained in preparation example 2, 15 parts by weight of an o-cresol formaldehyde resin, 25 parts by weight of a phenoxy resin, 10 parts by weight of a blocked isocyanate curing agent (TAKENATE B-820NP) and 8 parts by weight of a phosphorus-containing flame retardant (OP-930).
The above components are first adjusted with ethyl acetate to form a liquid dispersion (solid content: 40%), and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PBT insulating film with the thickness of 150 mu m by a coating machine, wherein the coating thickness is 10 mu m; and then treated at 150 ℃ for 5 minutes to volatilize the solvent, and a partially cured resin composition layer is formed on the PBT insulating film, so that the insulating adhesive film for the laminated busbar is obtained.
Comparative example 3
A resin composition comprises 50 parts by weight of copolyamide obtained in preparation example 3, 8 parts by weight of phenolic novolac resin, 30 parts by weight of phenoxy resin, 10 parts by weight of blocked isocyanate curing agent (Desmodur BL3175SN) and 10 parts by weight of phosphorus-containing flame retardant (OP-935).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Comparative example 4
A resin composition comprising, by weight, 48 parts of the copolyamide obtained in preparation example 4, 28 parts of a phenol aralkyl resin, 27 parts of a phenoxy resin, 9 parts of pyromellitic dianhydride, and 5 parts of a phosphorus-containing flame retardant (SP-703H).
The components are adjusted by propylene glycol monomethyl ether acetate to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a NOMEX insulating film with the thickness of 250 μm by using a coating machine, wherein the coating thickness is 50 μm; then, the resultant was treated at 160 ℃ for 2 minutes to volatilize the solvent, thereby forming a partially cured resin composition layer on the NOMEX insulating film, thereby obtaining an insulating adhesive film for laminated busbars.
Comparative example 5
A resin composition comprising, by weight, 48 parts of the copolyamide obtained in preparation example 4, 18 parts of a phenol aralkyl resin, 15 parts of a phenoxy resin, 9 parts of pyromellitic anhydride, and 5 parts of a phosphorus-containing flame retardant (SP-703H).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Comparative example 6
A resin composition comprising, by weight, 48 parts of the copolyamide obtained in preparation example 4, 18 parts of a phenol aralkyl resin, 35 parts of a phenoxy resin, 9 parts of pyromellitic dianhydride, and 5 parts of a phosphorus-containing flame retardant (SP-703H).
The components are adjusted by propylene glycol monomethyl ether acetate to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a NOMEX insulating film with the thickness of 250 μm by using a coating machine, wherein the coating thickness is 50 μm; then, the resultant was treated at 160 ℃ for 2 minutes to volatilize the solvent, thereby forming a partially cured resin composition layer on the NOMEX insulating film, thereby obtaining an insulating adhesive film for laminated busbars.
Comparative example 7
A resin composition comprising, by weight, 50 parts of the copolyamide obtained in preparation comparative example 1, 20 parts of a phenol novolac resin, 30 parts of a phenoxy resin, 10 parts of methylhexahydrophthalic anhydride, and 10 parts of a phosphorus-containing flame retardant (OP-935).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Comparative example 8
A resin composition comprising, by weight, 45 parts of the copolyamide obtained in preparation comparative example 2, 15 parts of an o-cresol novolac resin, 25 parts of a phenoxy resin, 10 parts of a blocked isocyanate curing agent (TAKENATE B-820NP), and 8 parts of a phosphorus-containing flame retardant (OP-930).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Comparative example 9
A resin composition comprising, by weight, 48 parts of the copolyamide obtained in preparation comparative example 3, 18 parts of a phenol aralkyl resin, 27 parts of a phenoxy resin, 9 parts of pyromellitic dianhydride, and 5 parts of a phosphorus-containing flame retardant (SP-703H).
The components are adjusted by toluene and n-butanol to form liquid dispersion (solid content is 50 percent) and mixed to prepare the halogen-free resin composition. The halogen-free resin composition is applied to an insulating adhesive film for a laminated busbar.
Coating the halogen-free resin composition on a PEN insulating film with the thickness of 190 μm by a coating machine, wherein the coating thickness is 40 μm; then, the film was treated at 100 ℃ for 10 minutes to volatilize the solvent and form a partially cured resin composition layer on the PEN insulating film, thereby obtaining an insulating film for laminated busbars.
Comparative example 10
A resin composition comprising, by weight, 40 parts of the copolyamide obtained in preparation comparative example 4, 10 parts of bisphenol A phenol resin, 20 parts of phenoxy resin, 5 parts of tetrahydrophthalic anhydride, and 10 parts of a phosphorus-containing flame retardant (SPB-100).
The copolyamide resin has too high crystallinity to be dissolved by a solvent, and a liquid resin composition cannot be obtained for coating to prepare an insulating adhesive film.
And (3) carrying out performance test on the prepared insulating adhesive film, wherein the test method of each test item is as follows:
(1) peel strength
The adhesion between the insulating adhesive film and the copper foil is subjected to 180-degree stripping test; wherein, the A-state peel strength is a test result in air, and the high-temperature peel strength is a test result in silicone oil at a corresponding temperature.
(2) Electric strength
And after the insulating adhesive film is connected with equipment, applying voltage with the frequency of 50Hz, and calculating the electric strength during breakdown.
(3) Dimensional stability
Treating the insulating adhesive film at 125 ℃ for 4 hours and at 150 ℃ for 2 hours, and then measuring the dimensional changes of the insulating adhesive film in the MD and TD directions before and after the treatment; wherein MD is the radial direction and TD is the latitudinal direction.
(4) Cold and hot shock performance
And (4) pressing the insulating adhesive film and the copper bar at a high temperature, and then carrying out a cold and hot shock test. The cold and hot impact test conditions are as follows: 40 ℃ to 130 ℃/1000 cycles, 40 ℃/constant temperature for 2 hours, 40 ℃ temperature to 130 ℃/1 minute, 130 ℃/constant temperature for 2 hours, 130 ℃ temperature to-40 ℃/1 minute, the above cycle is about 4 hours.
After the cold and hot impact, no bubble or crack exists between the adhesive film and the copper bar, the copper bar is qualified, and otherwise, the copper bar is unqualified.
(5) Humid heat aging property
And (4) pressing the insulating adhesive film and the copper bar at a high temperature, and then carrying out a damp-heat aging test. The damp-heat aging test conditions are as follows: 85 ℃ X85% RH/2000 hours.
And after the wet heat aging, the glue film and the copper bar are qualified if no bubble, delamination or cracking exists, or are unqualified.
(6) Processability (bending test)
And (3) pressing the copper bar with the thickness of 3mm and the adhesive film at high temperature, cooling to room temperature, and performing a bending test, wherein the bending angle is 150 degrees.
(7) High temperature testing
And (3) placing the bent sample in an oven at 130 ℃ for baking for 2000 hours, wherein the adhesive film and the copper bar are qualified if no bubble, delamination or cracking exists, and are not qualified if no bubble, delamination or cracking exists.
(8) Flame retardancy
Measured according to the UL94 vertical burning method.
The specific test results are shown in tables 3 and 4 below:
TABLE 3
TABLE 4
As can be seen from tables 3 and 4, in the embodiment, the resin composition prepared by mixing the copolyamide, the phenolic resin, the phenoxy resin, the curing agent and the flame retardant with reasonable proportion and structure is coated on the surface of the insulating base film to obtain the halogen-free environment-friendly insulating adhesive film with excellent flexibility and heat resistance, the peel strength of the a state is greater than 2.0N/mm, the peel strength of the a state is greater than 1.0N/mm, the cracking and foaming phenomena are not generated after the insulating adhesive film is subjected to 1000 high and low temperature impact cycles, wet heat aging for 2000 hours under 85 ℃ and 85% humidity conditions and high temperature test for 2000 hours, and the application requirement of the laminated busbar with the working temperature of 130 ℃ can be completely met. In addition, the insulation adhesive films prepared in examples 1 to 4 are inferior to those prepared in examples 5 to 8 in terms of high and low peel strength and electrical strength, because examples 1 to 4 use blocked isocyanate curing agents and anhydride curing agents used in examples 5 to 8, and the blocked isocyanate curing agents release small molecules to form micro bubbles in the adhesive layer when unblocked at high temperature, resulting in deterioration of the adhesiveness, heat resistance and insulation properties of the insulation adhesive films. In comparative examples 1 to 10, the copolyamide resin structure or the proportion of the components of the composition is not within the range defined by the invention, so that a resin composition with excellent comprehensive performance cannot be obtained, the peel strength in the A state and the peel strength at 130 ℃ are far lower than those of the resin composition in the examples, the resin composition is not qualified in cold and hot impact, humid and hot aging, processability and high temperature tests, and the application requirement of a high-reliability laminated busbar with the working temperature of 130 ℃ cannot be met.
The applicant states that the resin composition, the insulating adhesive film for laminated busbars containing the resin composition and the preparation method thereof are described by the above examples, but the invention is not limited to the above examples, i.e. the invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (16)
1. A resin composition characterized by comprising a copolyamide resin, a phenol resin, a phenoxy resin, a curing agent and a flame retardant dispersed in an organic solvent;
the content of each component in the resin composition is as follows: 40-50 parts of copolyamide resin, 10-20 parts of phenolic resin, 20-30 parts of phenoxy resin, 5-10 parts of curing agent and 5-10 parts of flame retardant;
the copolyamide resin is obtained by the polycondensation of dibasic acid and diamine;
the molar ratio of the dibasic acid to the diamine is 1: 1.05-1.1; the amine value of the copolyamide resin is 7-15 mgKOH/g;
the dibasic acid comprises more than 50 mol% of non-aromatic dibasic acid and less than 50 mol% of aromatic dibasic acid; the diamine comprises more than 80 mol% of non-aromatic diamine and less than 20 mol% of aromatic diamine;
the glass transition temperature of the copolyamide resin is 10-40 ℃; the crystallinity of the copolyamide resin is 10-18 percent; the number average molecular weight of the copolyamide resin is 8000-12000.
2. The resin composition of claim 1, wherein the resin composition has a solids content of 30 wt% to 60 wt%.
3. The resin composition of claim 1, wherein the non-aromatic dibasic acid comprises one or a combination of at least two of succinic acid, adipic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid;
the aromatic dibasic acid comprises one or the combination of at least two of terephthalic acid, phthalic acid and isophthalic acid;
the non-aromatic diamine comprises one or a combination of at least two of ethylenediamine, bis (3-methyl-4-aminocyclohexyl) methane or p-bis (aminocyclohexyl) methane;
the aromatic diamine comprises one or the combination of at least two of p-phenylenediamine, 4 '-diaminodiphenyl ether or 2,2' -bis [4- (4-aminophenoxy) phenyl ] propane.
4. The resin composition according to claim 1, wherein the phenolic resin is a phenol novolac resin.
5. The resin composition according to claim 1, wherein the phenolic resin is any one of or a mixture of at least two of a bisphenol a type phenolic resin, an o-cresol formaldehyde resin, a phenol phenolic resin, an aralkyl phenolic resin, a novolac type phenolic resin, or a triazine structure-containing phenolic resin.
6. The resin composition of claim 1, wherein the phenoxy resin has the following structural formula:
wherein R is1、R2、R3、R4represents-H, -Br or a P-containing group, R1、R2、R3、R4Represent the same or different groups; n represents an integer of 50 to 150.
7. The resin composition according to claim 1, wherein the curing agent is one or both of a blocked isocyanate curing agent and an acid anhydride curing agent.
8. The resin composition of claim 7, wherein the blocked isocyanate curing agent has a deblocking temperature of 80 ℃ to 160 ℃.
9. The resin composition according to claim 7, wherein the acid anhydride curing agent is any one of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic dianhydride, or a combination of at least two thereof.
10. The resin composition according to claim 1, wherein the flame retardant is a phosphorus-containing flame retardant.
11. The resin composition of claim 10, wherein the phosphorus-containing flame retardant is any one of flame retardant SPB-100, flame retardant OP-930, flame retardant OP-935, or flame retardant SP-703H, or a combination of at least two thereof.
12. The resin composition according to claim 1, wherein the organic solvent is one or a combination of at least two of ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, cyclohexanol, isoamyl alcohol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, butanone, acetone, cyclohexanone, toluene, xylene, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or ethyl acetate.
13. An insulating adhesive film for a laminated busbar, comprising an insulating thin film and the resin composition according to any one of claims 1 to 12 coated on the insulating thin film;
the insulating film is any one of a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polyimide film or a polyisophthaloyl metaphenylene diamine film.
14. The insulating adhesive film for the laminated busbar according to claim 13, wherein the thickness of the insulating film is 100 to 250 μm, and the thickness of the resin composition coated on the insulating film is 10 to 50 μm.
15. The method for preparing the insulating adhesive film for the laminated busbar according to claim 13 or 14, wherein the method comprises the following steps:
(1) dispersing copolyamide resin, phenolic resin, phenoxy resin, a curing agent and a flame retardant in an organic solvent to obtain a resin composition;
(2) and (2) coating the resin composition obtained in the step (1) on an insulating film, and drying to obtain the insulating glue film for the laminated busbar.
16. The preparation method of claim 15, wherein the drying in the step (2) is realized by an online drying oven, and the drying is carried out by heating at 80-160 ℃ for 2-10 minutes.
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| JP2013087165A (en) * | 2011-10-17 | 2013-05-13 | Nippon Zeon Co Ltd | Insulating adhesive film, laminate, cured material, and printed wiring board |
| CN106700428A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film |
| CN108753167A (en) * | 2018-05-15 | 2018-11-06 | 广东生益科技股份有限公司 | A kind of resin combination, the stack bus bar insulated rubber film and preparation method thereof comprising it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013087165A (en) * | 2011-10-17 | 2013-05-13 | Nippon Zeon Co Ltd | Insulating adhesive film, laminate, cured material, and printed wiring board |
| CN106700428A (en) * | 2016-12-29 | 2017-05-24 | 广东生益科技股份有限公司 | Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film |
| CN108753167A (en) * | 2018-05-15 | 2018-11-06 | 广东生益科技股份有限公司 | A kind of resin combination, the stack bus bar insulated rubber film and preparation method thereof comprising it |
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