CN106700428A - Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film - Google Patents
Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film Download PDFInfo
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- CN106700428A CN106700428A CN201611246829.5A CN201611246829A CN106700428A CN 106700428 A CN106700428 A CN 106700428A CN 201611246829 A CN201611246829 A CN 201611246829A CN 106700428 A CN106700428 A CN 106700428A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/62—Insulating-layers or insulating-films on metal bodies
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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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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention provides a halogen-free resin composition. The halogen-free resin composition comprises the following components in parts by mass: 40-110 parts of saturated polyester resin, 5-40 parts of phenolic resin, 1-20 parts of a curing agent, 10-150 parts of a halogen-free flame retardant, 0-100 parts of a filler, 0.01-1 part of an antioxidant and 0.01-5 parts of a coupling agent. In the halogen-free resin composition, the phenolic resin has good flame retardance and excellent heat resistance, and both the saturated polyester resin and the phenolic resin contain hydroxyl groups and can react with the curing agent to form an interpenetrating polymer network, so that the obtained cured product system has excellent high-temperature adhesion and flame retardance. The invention further provides an adhesive and a laminated busbar insulating adhesive film prepared from the halogen-free resin composition, and a preparation method of the laminated busbar insulating adhesive film.
Description
Technical field
Insulated rubber film field is used the present invention relates to stack bus bar, more particularly to a kind of halogen-free resin composition and its preparation
Adhesive, stack bus bar insulated rubber film, the preparation method of the insulated rubber film.
Background technology
Stack bus bar is also referred to as composite bus bar, composite bus, laminated bus, composite copper bar, low-inductance bus etc., its English name quilt
Referred to as Laminatd Busbar.It is arranged as a kind of connection with multi-level composite construction, and stack bus bar can be regarded as distribution
The highway of system.Wiring method that is heavy with traditional complexity and taking time and effort is compared, and stack bus bar can provide skill high
Art content and easily design the distribution system of clear structure.It is low, anti-interference that it possesses repeatable electric property, inductive impedance
The Some features such as ability is strong and reliability is high, therefore, it can be as the electric connecting part of some high power modules.This
Outward, the features such as having simple assembling, compact conformation due to stack bus bar, it is widely used in wind-powered electricity generation, photovoltaic, electric propulsion and sets
Power conversion module of standby and catenet equipment etc..
Stack bus bar is mainly formed by conductor material and insulating materials through hot pressing, typically using copper, aluminium as conductor material,
Then using insulated rubber film is as bonding and insulate between conductor material；As the insulating cement bonded between conductor with insulating materials
Film, the quality of its performance has vital influence for the performance quality of stack bus bar.Currently, for the exhausted of stack bus bar
The adhesive of edge glued membrane mainly has epoxies adhesive and saturated polyester class adhesive.Epoxies adhesive is a class thermosetting cement
Stick, has the advantages that good adhesive property, Good Heat-resistance, electrical insulation capability be good, dielectric properties are excellent, but there is also storage
Deposit the shortcomings of phase is short, pressing time is long, pressing-in temp is high so that its application in stack bus bar insulated rubber film is limited
System.Saturated polyester class adhesive is an analog thermoplastic adhesive, although have the advantages that storage time is long, pressing time is short, but
Be saturated polyester class adhesive high temperature bonding performance it is typically poor, it is also difficult to meet stack bus bar insulated rubber film application will
Ask.
In order to improve the high temperature bonding performance of saturated polyester class adhesive, at present generally using with epoxy blend or
The mode of a small amount of curing agent is added, interpenetrating polymer networks structure is formed it into or is produced partial cross-linked to improve saturated polyester
The resistance to elevated temperatures of class adhesive.It is gluing that such as Chinese patent CN104178044A discloses a kind of epoxide modified saturated polyester resin
Agent, is prepared from by each component of following mass percent：Saturated polyester resin A20-50%, saturated polyester resin B5-30%,
Epoxy resin 2-20%, isocyanates 1-10%, fire retardant 20-70%, dispersant 0.05-5%, being scattered in by said ratio has
In machine solvent, stack bus bar modified saturated polyester adhesive is obtained.But epoxy resin open loop and the reaction temperature of isocyanates
Degree is usually above 200 DEG C, is difficult to form interpenetrating polymer networks structure to improve saturation with saturated polyester resin under compared with low temperature
The high-temperature behavior of polyester adhesive system.And for example Chinese patent CN105176468A and CN105199649A then disclose one kind and adopt
Saturated polyester resin forming part is crosslinked with the method for addition anhydride curing agent, but totally still keeps thermoplasticity, can be notable
Improve the high temperature bonding performance of saturated polyester adhesive.But this modified saturated polyester adhesive can only be used to operating temperature and be
105 DEG C of stack bus bar, as temperature is raised, the high temperature bonding intensity of the saturated polyester adhesive is reduced rapidly, it is impossible to met
The more application requirement of elevated operating temperature stack bus bar.
Additionally, can be divided mainly into halogen type and halogen-free type for the insulated rubber film of stack bus bar.However, with various environmental protection
The promulgation of laws and regulations and Public environmental attitude are improved, and the use for having halogen type product is increasingly restricted, and halogen-free type is produced
The exploitation of product has been then trend of the times with application.
The content of the invention
An object of the present invention is to provide a kind of halogen-free resin composition；The second object of the present invention is offer one
Plant the adhesive made using above-mentioned halogen-free resin composition；The third object of the present invention is to provide a kind of using above-mentioned Halogen
The stack bus bar insulated rubber film that resin combination makes；The fourth object of the present invention is that the stack bus bar described in offer uses exhausted
The preparation method of edge glued membrane.Described stack bus bar with insulated rubber film use above-mentioned halogen-free resin composition, its good flame retardation effect,
With excellent high temperature peel strength, processing characteristics and high/low-temperature impact performance, more elevated operating temperature stack bus bar can be met
Application requirement and increasingly strict environmental requirement.
To realize the purpose, the present invention provides a kind of halogen-free resin composition, according to mass fraction meter, the Halogen resin
Composition include 40~110 parts of saturated polyester resin, for example, 41 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 80
Part, 90 parts, 100 parts, 105 parts or 109 parts；5~40 parts of phenolic resin, for example, 6 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30
Part, 35 parts or 39 parts；1~20 part of curing agent, for example, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 19 parts；And halogen-free flame retardants 10
~150 parts, for example, 11 parts, 15 parts, 25 parts, 35 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts,
130 parts, 140 parts or 149 parts.
Halogen-free resin composition of the invention, as matrix resin, coordinates phenolic resin, solidification using saturated polyester resin
Agent and halogen-free flame retardants are constituted, and wherein phenolic resin has good anti-flammability and excellent heat resistance, and saturated polyester resin
With contain hydroxyl in phenolic resin, can all be reacted with curing agent, formed interpenetrating polymer networks, so as to get solidification objects system
With excellent high temperature bonding performance.
The molecular weight of saturated polyester resin is too high, then dissolve difficult, and obtained resin combination viscosity is too high, causes to apply
Cover apparent poor；The molecular weight of saturated polyester resin is too low, then the cohesive strength of resin composition layer is relatively low after coating, and causes stripping
From insufficient strength.Saturated polyester hydroxyl value is too low, then cannot form three-dimensional crosslinked network with phenolic resin, curing agent；Saturated polyester
Hydroxyl value is too high, then crosslink density is too high, and resin composition layer becomes fragile.
It is preferred that the saturated polyester resin include saturated polyester resin A or saturated polyester resin B in any one or
Both mixtures；The molecular weight Mn of the saturated polyester resin A between 3000~30000, glass transition temperature Tg-
Between 30~65 DEG C, such as -30 DEG C, -20 DEG C, -10 DEG C, 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 50 DEG C or 65 DEG C；Hydroxyl value 2~
Between 15mgKOH/g, such as 2mgKOH/g, 5mgKOH/g, 10mgKOH/g or 15mgKOH/g；The saturated polyester resin B's
Molecular weight Mn between 5000~30000, glass transition temperature Tg between 10~110 DEG C, for example：11℃、15℃、20
DEG C, 30 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C or 109 DEG C；Hydroxyl value between 2~15mgKOH/g, for example
2.5mgKOH/g, 5mgKOH/g, 10mgKOH/g or 14mgKOH/g.According to mass fraction meter, the saturated polyester resin A's adds
Dosage is 0~30 part, can be 1 part, 5 parts, 10 parts, 20 parts, 25 parts or 29 parts；The addition of the saturated polyester resin B is
40~80 parts, can be 41 parts, 50 parts, 60 parts, 70 parts or 79 parts.The saturated polyester resin A can preferred SK Chemical of South Korea
S1611, S1426, S1313 of ES450, ES850, ES750 of manufacture, also Evonik companies of Germany manufacture etc.；Described is full
L952, L912 manufactured with Evonik companies of polyester resin B preferable Germany etc., the also ES901 of SK Chemical of South Korea manufacture,
ES600, ES120 etc..
It is preferred that the phenolic resin may be selected from thermosetting phenolic resin or thermoplastic phenolic resin any one or
Two kinds of mixture.
It is preferred that pressing structure choice, the phenolic resin may be selected from bisphenol A type phenolic resin, o-cresol-formaldehyde resin, phenol
In phenolic resin, aralkyl phenolic resin, promise volt clarke type phenolic resin, the phenolic resin containing triazine structure any one or
At least two mixture.
It is preferred that pressing structure choice, it is solid that the curing agent is selected from aliphatic isocyanates curing agent, alicyclic isocyanate
In agent, aromatic isocyanate curing agent any one or at least two mixture；The aliphatic isocyanates are consolidated
Agent is selected from any one or at least two in hexamethylene diisocyanate (HDI) dimer, tripolymer or addition product
Mixture；The alicyclic isocyanate curing agent is selected from IPDI (IPDI) dimer, tripolymer or adds
Into any one in thing or at least two mixture；Described aromatic isocyanate curing agent is selected from toluene diisocynate
Ester (TDI) dimer, tripolymer or addition product, 2,4- methyl diphenylene diisocyanates (MDI) dimer, tripolymer or addition
Thing, in XDI (XDI) dimer, tripolymer or addition product any one or at least two mixing
Thing.
It is preferred that being selected by response characteristic, it is different that the curing agent is selected from room temperature reaction type isocyanate curing agent, enclosed type
One or both of cyanate curing agent mixture；The Blocked Isocyanate Curing Agents need high temperature just to possess after unsealing
Reactivity, described deblocking temperature is less than 140 DEG C.Deblocking temperature is too high, causes baking and pressing-in temp too high, brings energy consumption
Rise, and high temperature is pressed for a long time, can also cause thin polymer film hydraulic performance decline.
It is preferred that the halogen-free flame retardants can be phosphonium flame retardant, nitrogenous flame ratardant or the two combination.According to mass parts
Number meter, phosphonium flame retardant is 10~100 parts, for example, 11 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts
Or 99 parts, nitrogenous flame ratardant be 0~50 part, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 40 parts, 45 parts or
49 parts.The phosphonium flame retardant preferably uses the SPB-100 of Japanese big tomb strain formula chemistry manufacture, German Clariant Corporation manufacture
OP-930, OP-935, four countries are melted into SP-703H of Co., Ltd.'s manufacture etc..Because for preparing stack bus bar insulated rubber film
In addition to considering flame retarding efficiency, also need to consider that fire retardant impacts high/low temperature peel strength, wet and heat ageing resistant, high-low temperature resistant
The influence of the performances such as property, processability.
The nitrogenous flame ratardant is melamine and its salt, belongs to compound in triazine class, main by decomposition heat absorption and raw
Played a role with diluting combustible into fire retardant gas, this based flame retardant Halogen, low toxicity, low cigarette, but flame retarding efficiency is not good enough.This
Invention uses compound in triazine class to cooperate with phosphonium flame retardant to reach flame-retardancy requirements, and nitrogenous flame ratardant of the invention is preferably used
Ciba melapur series of products, such as melapur MC50, melapurMC25 and melapur MC15.
It is preferred that the halogen-free resin composition also includes filler, as mass fraction, described filler is 0~100 part,
Such as 1 part, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 99 parts；Described filler is hydroxide
It is any in aluminium, magnesium hydroxide, silica, magnesia, zeolite, wollastonite, clay, talcum, mica, calcium carbonate and calcium silicates
It is a kind of or at least two mixture.
It is preferred that the halogen-free resin composition also includes antioxidant, according to mass fraction meter, the addition of the antioxidant
Measure is 0.01~1 part.Stack bus bar insulated rubber film service life can be extended, slow down or suppress adhesive ageing process during hot pressing
Carrying out, the present invention in preferably use Hinered phenols antioxidant 1010,1076,1098,2246 and phosphite ester kind antioxidant
168、618。
It is preferred that the halogen-free resin composition also includes coupling agent, according to mass fraction meter, the addition of the coupling agent
It is 0.01~5 part to measure, and the coupling agent is the mixture of any one or two kinds in silane coupler, titanate coupling agent,
The silane coupler be KH171, KH151, KH172, KH792, KH550, KH560, KH570, KH530 in any one or
At least two mixture；The titanate coupling agent be TMC-101, TMC-102, TMC-201, TMC-105, TMC-311w,
In TMC-311, TMC-2 any one or at least two mixture.
The present invention also provides a kind of burning-resistant type adhesive, including halogen-free resin composition as described above and organic solvent,
The solid content of the burning-resistant type adhesive be 20wt%~60wt%, preferably 30wt%~60wt%, for example：30wt%,
40wt%, 50wt% or 60wt%；Suitable viscosity can be obtained, there is provided good processability, it is ensured that use (as coated) process
In occur without visual defects.
It is preferred that the organic solvent is butanone, acetone, cyclohexanone, toluene, dimethylbenzene, glycol monoethyl ether, propane diols
In monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate any one or at least two mixture.
The present invention also provides a kind of stack bus bar insulated rubber film, including insulation film and single or double be coated on it is described
The gluing oxidant layer that burning-resistant type adhesive as described above on insulation film is formed.
It is preferred that the insulation film is pet film (PET), polybutylene terephthalate
Ester film (PBT), PEN film (PEN), Kapton (PI) or it is poly- between phenyl-diformyl isophthalic two
Amine film (NOMEX).
It is preferred that the thickness of the insulation film is 100~250 μm, for example：105μm、110μm、120μm、130μm、
140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm or 249 μm；
The thickness of the gluing oxidant layer is 10~50 μm, for example：11 μm, 20 μm, 30 μm, 40 μm or 49 μm.
The present invention also provides a kind of method for preparing stack bus bar insulated rubber film as described above, it is characterised in that bag
Include step：
(1) saturated polyester resin, phenolic resin, curing agent, phosphonium flame retardant, nitrogenous resistance are weighed according to the mass fraction
Combustion agent, filler, antioxidant and coupling agent, high shear dispersed with stirring is used cooperatively using ball mill, jar mill or sand mill simultaneously
Equipment mixes it with organic solvent, and burning-resistant type adhesive is obtained；And
(2) the burning-resistant type adhesive single or double is coated on insulating substrate, online drying oven is sent into, 80
~160 DEG C are heated 2~10 minutes to remove the organic solvent, form the gluing oxidant layer of solid-state, and winding obtains the lamination
Busbar insulated rubber film.
It is preferred that the organic solvent is butanone, acetone, cyclohexanone, toluene, dimethylbenzene, glycol monoethyl ether, propane diols
In monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate any one or at least two mixture.
Prior art is compared, and the present invention has the advantages that：
A small amount of phenolic resin is added in halogen-free resin composition of the invention, virtue can be introduced in halogen-free resin composition
Ring, improves heat resistance and fire resistance.Phenolic resin and saturated polyester resin all contain hydroxyl simultaneously, can all occur with curing agent
Cross-linking and curing reaction, so as to form interpenetrating polymer networks, what is obtained solidifies the excellent heat resistance of objects system and high temperature bonding
Energy.The anti-flammability of the stack bus bar insulated rubber film prepared using the halogen-free resin composition is had up to UL94VTM-0 grades
Excellent high temperature peel strength, dimensional stability, processing characteristics and high/low-temperature impact performance, can meet more elevated operating temperature lamination
The application requirement of busbar.Using halogen-free flame retardants, increasingly strict environmental requirement can be met.
Figure of description
Fig. 1 is the schematic diagram of stack bus bar insulated rubber film first embodiment of the present invention.
Fig. 2 is the schematic diagram of stack bus bar insulated rubber film second embodiment of the present invention.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of halogen-free resin composition, including 40 parts of saturated polyester resin B (L952), the thermoplastic calculated according to mass fraction
5 parts of phenolic resin of property, 3 parts of aliphatic isocyanates curing agent, 30 parts of phosphonium flame retardant (OP-935), filler (aluminium hydroxide) 5
Part, (168) 0.3 parts of antioxidant, 0.8 part of coupling agent (KH570).
Described halogen-free resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described with cyclohexanone
Saturated polyester resin B, thermoplastic phenolic resin, aliphatic isocyanates curing agent, phosphonium flame retardant, filler, antioxidant, coupling
The liquid dispersion (solids content 40wt%) of agent composition, is blended into burning-resistant type adhesive.
As shown in figure 1, the burning-resistant type adhesive coating machine one side is coated in into the PET insulation films that thickness is 125 μm again
On 10, rubberization thickness is 30 μm；
Then processed 5 minutes at 160 DEG C, so that cyclohexanone volatilizees, the gluing oxidant layer of solid-state is formed on PET dielectric films
10；
Finally winding obtains the stack bus bar insulated rubber film 1 of the halogen-free resin composition.
Embodiment 2
A kind of halogen-free resin composition, including 5 parts of saturated polyester resin A (S1611), the saturation calculated according to mass fraction
75 parts of polyester resin B (ES120), 15 parts of thermosetting phenolic resin, 20 parts of alicyclic isocyanate curing agent, phosphonium flame retardant
(SPB-100) 80 parts, 20 parts of nitrogenous flame ratardant (melapur MC15), 10 parts of filler (magnesium hydroxide), antioxidant (1010) 0.1
Part, 0.08 part of coupling agent (KH570).
Described halogen-free resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described full with acetone
With polyester resin A, saturated polyester resin B, thermosetting phenolic resin, alicyclic isocyanate curing agent, phosphonium flame retardant, nitrogenous
Fire retardant, filler, antioxidant, the liquid dispersion (solids content 45wt%) of coupling agent composition, are blended into burning-resistant type adhesive.
As shown in Fig. 2 being coated in the PBT insulation films that thickness is 100 μm by the burning-resistant type adhesive coating machine is two-sided again
On 10 ', rubberization thickness is 40 μm；
Then processed 5 minutes at 90 DEG C, so that acetone volatilizees, the gluing oxidant layer of solid-state is formed on PBT dielectric films
20’；
Finally winding obtains the stack bus bar insulated rubber film 1 ' of the halogen-free resin composition.
Embodiment 3
A kind of halogen-free resin composition, including 25 parts of saturated polyester resin A (S1426), the saturation calculated according to the mass fraction
40 parts of polyester resin B (L912), 30 parts of thermoplastic phenolic resin, 8 parts of aromatic isocyanate curing agent, phosphonium flame retardant (SP-
703H) 30 parts, 40 parts of nitrogenous flame ratardant (melapur MC15), 20 parts of filler (silica), (1010) 0.5 parts of antioxidant,
0.2 part of coupling agent (TMC-311).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by institute with ethyl acetate
State saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, aromatic isocyanate curing agent, phosphonium flame retardant,
Nitrogenous flame ratardant, filler, antioxidant, the liquid dispersion (solids content is 50wt%) of coupling agent composition, are blended into flame retardant type
Adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PEN insulation films that thickness is 100 μm again, rubberization thickness
It is 30 μm；
Then processed 5 minutes at 90 DEG C, so that ethyl acetate volatilizees, the adhesive of solid-state is formed on PEN dielectric films
Layer；
Finally winding obtains the stack bus bar insulated rubber film of the halogen-free resin composition.
Embodiment 4
A kind of halogen-free resin composition, including calculate according to the mass fraction 8 parts of saturated polyester resin A (ES450), saturation gather
47 parts of ester resin B (L952), 8 parts of thermosetting phenolic resin, 5 parts of aliphatic isocyanates curing agent, phosphonium flame retardant (SP-
730H) 45 parts, 17 parts of nitrogenous flame ratardant (melapur MC25), (1076) 0.9 parts of antioxidant, 10 parts of filler (aluminium hydroxide),
0.07 part of coupling agent (KH171).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described full with butanone
With polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aliphatic isocyanates curing agent, phosphonium flame retardant, nitrogenous
Fire retardant, antioxidant, filler, the liquid dispersion (solids content is 60wt%) of coupling agent composition, are blended into flame retardant type gluing
Agent.
The burning-resistant type adhesive coating machine one side is coated on the PI insulation films that thickness is 110 μm again, rubberization thickness
It is 12 μm；
Then processed 9 minutes at 110 DEG C, so that butanone volatilizees, the gluing oxidant layer of solid-state is formed on PI dielectric films；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 5
A kind of halogen-free resin composition, including 11 parts of saturated polyester resin A (ES850), the saturation calculated according to the mass fraction
68 parts of polyester resin B (L912), 14 parts of thermoplastic phenolic resin, 8 parts of alicyclic isocyanate curing agent, phosphonium flame retardant (OP-
930) 55 parts, it is 19 parts of nitrogenous flame ratardant (melapur MC50), (1098) 0.4 parts of antioxidant, 30 parts of filler (silica), even
3.8 parts of connection agent (KH151).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described full with acetone
With polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, alicyclic isocyanate curing agent, phosphonium flame retardant, nitrogenous
Fire retardant, antioxidant, filler, the liquid dispersion (solids content is 45wt%) of coupling agent composition, are blended into flame retardant type gluing
Agent.
The burning-resistant type adhesive coating machine one side is coated on the NOMEX insulation films that thickness is 130 μm again, gluing is thick
Spend is 17 μm；
Then processed 7 minutes at 165 DEG C, so that acetone volatilizees, the adhesive of solid-state is formed on NOMEX dielectric films
Layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 6
A kind of halogen-free resin composition, including 29 parts of saturated polyester resin A (ES750), the saturation calculated according to the mass fraction
72 parts of polyester resin B (ES901), 19 parts of thermosetting phenolic resin, 19 parts of aromatic isocyanate curing agent, phosphonium flame retardant
(OP-935) 60 parts, it is 22 parts of nitrogenous flame ratardant (melapur MC50), (618) 1 parts of antioxidant, 70 parts of filler (magnesia), even
2.6 parts of connection agent (KH172).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described full with toluene
With polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aromatic isocyanate curing agent, phosphonium flame retardant, nitrogenous
Fire retardant, antioxidant, filler, the liquid dispersion (solids content is 57wt%) of coupling agent composition, are blended into flame retardant type gluing
Agent.
The burning-resistant type adhesive coating machine one side is coated on the PET insulation films that thickness is 150 μm again, rubberization thickness
It is 20 μm；
Then processed 6 minutes at 150 DEG C, so that toluene volatilizees, the gluing oxidant layer of solid-state is formed on PET dielectric films；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 7
A kind of halogen-free resin composition, including 17 parts of saturated polyester resin A (S1611), the saturation calculated according to the mass fraction
59 parts of polyester resin B (ES600), 24 parts of thermoplastic phenolic resin, 11 parts of aliphatic isocyanates curing agent, phosphonium flame retardant
(SPB-100) 75 parts, 24 parts of nitrogenous flame ratardant (melapur MC15), (1010) 0.5 parts of antioxidant, 60 parts of filler (zeolite),
4.7 parts of coupling agent (KH792).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described with dimethylbenzene
Saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, aliphatic isocyanates curing agent, phosphonium flame retardant, contain
Nitrogen combustion inhibitor, antioxidant, filler, the liquid dispersion (solids content is 53wt%) of coupling agent composition, are blended into flame retardant type glue
Stick.
The burning-resistant type adhesive coating machine one side is coated on the PBT insulation films that thickness is 140 μm again, rubberization thickness
It is 31 μm；
Then processed 7 minutes at 145 DEG C, so that dimethylbenzene volatilizees, the adhesive of solid-state is formed on PBT dielectric films
Layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 8
A kind of halogen-free resin composition, including 22 parts of saturated polyester resin A (S1426), the saturation calculated according to the mass fraction
70 parts of polyester resin B (ES120), 33 parts of thermosetting phenolic resin, 15 parts of alicyclic isocyanate curing agent, phosphonium flame retardant
(SP-703H) 65 parts, 37 parts of nitrogenous flame ratardant (melapur MC25), (1076) 0.7 parts of antioxidant, 50 parts of filler (clay),
3.1 parts of coupling agent (KH550).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First spent glycol monomethyl ether regulation
By the saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, alicyclic isocyanate curing agent, phosphorous resistance
Combustion agent, nitrogenous flame ratardant, antioxidant, filler, the liquid dispersion (solids content is 41wt%) of coupling agent composition, are blended into resistance
Combustion type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PEN insulation films that thickness is 160 μm again, rubberization thickness
It is 38 μm；
Then processed 6 minutes at 130 DEG C, so that glycol monoethyl ether volatilizees, the glue of solid-state is formed on PEN dielectric films
Adhesive layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 9
A kind of halogen-free resin composition, including 14 parts of saturated polyester resin A (S1313), the saturation calculated according to the mass fraction
63 parts of polyester resin B (L952), 28 parts of thermoplastic phenolic resin, 13 parts of aromatic isocyanate curing agent, phosphonium flame retardant
(OP-930) 70 parts, it is 32 parts of nitrogenous flame ratardant (melapur MC25), (1098) 0.2 parts of antioxidant, 40 parts of filler (mica), even
1.4 parts of connection agent (KH560).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted with propylene glycol monomethyl ether
By the saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, aromatic isocyanate curing agent, phosphorous resistance
Combustion agent, nitrogenous flame ratardant, antioxidant, filler, the liquid dispersion (solids content is 37wt%) of coupling agent composition, are blended into resistance
Combustion type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PI insulation films that thickness is 175 μm again, rubberization thickness
It is 42 μm；
Then processed 4 minutes at 140 DEG C, so that propylene glycol monomethyl ether volatilizees, the glue of solid-state is formed on PI dielectric films
Adhesive layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 10
A kind of halogen-free resin composition, including 27 parts of saturated polyester resin A (ES450), the saturation calculated according to the mass fraction
78 parts of polyester resin B (ES901), 39 parts of thermosetting phenolic resin, 17 parts of aliphatic isocyanates curing agent, phosphonium flame retardant
(OP-935) 30 parts, 43 parts of nitrogenous flame ratardant (melapur MC50), (2246) 0.6 parts of antioxidant, 25 parts of filler (calcium carbonate),
0.03 part of coupling agent (KH530).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First use propylene glycol monomethyl ether acetic acid
Ester regulation by the saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aliphatic isocyanates curing agent,
Phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, filler, the liquid dispersion (solids content is 32wt%) of coupling agent composition, mix
It is made burning-resistant type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the NOMEX insulation films that thickness is 195 μm again, gluing is thick
Spend is 47 μm；
Then processed 3 minutes at 150 DEG C, so that propylene glycol monomethyl ether acetate is volatilized, formed on NOMEX dielectric films
The gluing oxidant layer of solid-state；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Comparative example 1
A kind of halogen-free resin composition, 28 parts of the saturated polyester resin A (ES450) that will be calculated according to the mass fraction, saturation are gathered
73 parts of ester resin B (ES120), 7 parts of aromatic isocyanate curing agent, 45 parts of phosphonium flame retardant (SPB-100), nitrogenous flame ratardant
30 parts of (melapur MC15), (1010) 0.2 parts of antioxidant, 0.3 part of coupling agent (KH570).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described full with butanone
With polyester resin A, saturated polyester resin B, aromatic isocyanate curing agent, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant,
The liquid dispersion (solids content is 43%) of coupling agent composition, is blended into burning-resistant type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PET insulation films that thickness is 150 μm again, rubberization thickness
It is 30 μm；
Then processed 5 minutes at 90 DEG C, so that butanone volatilizees, the gluing oxidant layer of solid-state is formed on PET dielectric films；
Finally winding obtains the stack bus bar insulated rubber film of the halogen-free resin composition.
Comparative example 2
A kind of halogen-free resin composition, 20 parts of the saturated polyester resin A (S1313) that will be calculated according to the mass fraction, saturation are gathered
60 parts of ester resin B (L912), 20 parts of thermosetting phenolic resin, 70 parts of phosphonium flame retardant (OP-935), (168) 0.3 parts of antioxidant,
0.1 part of coupling agent (KH550).
By the halogen-free resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing halogen-free resin composition：First adjusted by described full with toluene
With polyester resin A, saturated polyester resin B, thermosetting phenolic resin, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, coupling agent
The liquid dispersion (solids content is 48%) of composition, is blended into burning-resistant type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PET insulation films that thickness is 188 μm again, rubberization thickness
It is 30 μm；
Then processed 5 minutes at 120 DEG C, so that toluene volatilizees, the gluing oxidant layer of solid-state is formed on PET dielectric films；
Finally winding obtains the stack bus bar insulated rubber film of the halogen-free resin composition.
Comparative example 3
Stack bus bar insulated rubber film is obtained according to the embodiment 1~5 of Chinese patent CN104178044A, as right
Ratio 3, and it is tested by the following method.
Stack bus bar to embodiment 1~10, comparative example 1~3 and existing product carries out performance test with insulated rubber film, respectively
The method of testing of test event is as follows：
(1) peel strength
The cohesive force of insulated rubber film and Copper Foil, 90 ° of disbonded tests；Wherein, A states peel strength is aerial test knot
Really, high temperature peel strength is the test result in the silicone oil of relevant temperature.
(2) electrical strength
After insulated rubber film connection equipment, making alive, frequency is 50Hz, electrical strength when calculating punctures.
(3) elongation percentage
By ASTM D-882 standards, obtained using material stretch test machine test.
(4) dimensional stability
125 DEG C of insulated rubber film is processed 4 hours, and 150 DEG C are processed 2 hours, then measures MD and TD directions after its before processing
Change in size；Wherein, MD is for radially, TD is broadwise.
(5) high/low-temperature impact performance
By insulated rubber film and copper bar high-temperature laminating, high and low temperature impact test is then carried out.High and low temperature impact test condition
For：- 40 DEG C~125 DEG C/200 times circulations, -40 DEG C/constant temperature 0.5 hour, -40 DEG C are warming up to 125 DEG C/1 minute, 125 DEG C/constant temperature
0.5 hour, 125 DEG C were cooled to -40 DEG C/1 minute, the circulation about 1 hour of the above one.
It is otherwise unqualified then for qualified between glued membrane and copper bar without foaming, without cracking after high/low-temperature impact.
(6) hydrothermal aging performance
By insulated rubber film and copper bar high-temperature laminating, hydrothermal aging experiment is then carried out.Hydrothermal aging experimental condition is：85℃
× 85%RH/1000 hours.
After hydrothermal aging between glued membrane and copper bar without foaming, delamination, cracking then for qualified, it is otherwise unqualified.
(7) processability (bending test)
By thickness to be cooled to room temperature after the copper bar and glued membrane high-temperature laminating of 3mm, folding test is carried out, bending angle is
90°.After bending between glued membrane and copper bar without foaming, delamination, cracking then for qualified, it is otherwise unqualified.
(8) high temperature test
The sample of Bending Processing is placed in into 125 DEG C of baking ovens to toast 240 hours, without foaming, delamination, cracking between glued membrane and copper bar
It is otherwise unqualified then for qualified.
(9) anti-flammability
Determined according to the vertical combustions of UL 94.
Specific test result is as shown in table 1 below.
As it can be seen from table 1 without with phenolic resin modified in halogen-free resin composition in comparative example 1, it is prepared
The A states peel strength of insulated rubber film is 1.73N/mm, in 105 DEG C of peel strengths also up to 0.93N/mm, and 125 DEG C of stripping
Intensity but only has 0.07N/mm；Phenolic resin is added in halogen-free resin composition in comparative example 2, but is not added with curing agent,
Inierpeneirating network structure cannot be formed, its A state peel strength is only 1.03N/mm, 105 DEG C of peel strengths are 0.41N/mm, 125 DEG C
Peel strength is 0.12N/mm, far below comparative example 1；Comparative example 1 and comparative example 2 cannot effectively draw the aromatic ring of phenolic resin
Enter in resin combination, to form three-dimensional crosslinked network, therefore use the high temperature of the insulated rubber film of resin combination preparation to peel off
Intensity is substantially less than embodiment, and high/low-temperature impact test, high temperature test and hydrothermal aging test are unqualified.Comparative example 3 is used
The embodiment of Chinese patent CN104178044A, because epoxy resin open loop and isocyanate curing agent reaction temperature generally exist
More than 200 DEG C, therefore epoxy resin cannot carry out effective cross-linking reaction at a lower temperature, cause addition epoxy resin to improving
The heat resistance effect of saturated polyester is very limited, and prepared insulated rubber film can only meet 105 DEG C of application requirements of stack bus bar,
It is unqualified in 125 DEG C of high temperature tests and high/low-temperature impact circulation.And add in the halogen-free resin composition of embodiment 1~10
Add phenolic resin modified, its high temperature bonding performance, high/low-temperature impact performance, hydrothermal aging performance are both with respect to comparative example 1~3
Be greatly improved, in 125 DEG C of environment peel strength still greater than 1.0N/mm, 200 high/low-temperature impacts circulations of experience, 85 DEG C and
Hydrothermal aging 1000 hours, high-temperature baking be after 240 hours under conditions of 85% humidity, cracking not yet, foaming phenomena.With phenol
Urea formaldehyde modified saturated polyester resin, contains hydroxyl in phenolic resin and saturated polyester resin, and all can be solid with isocyanates
Agent crosslinks reaction, forms interpenetrating polymer networks, is remarkably improved heat resistance and the high temperature stripping of saturated polyester adhesive
From intensity.
In sum, the electrical resistance of halogen-free resin composition of the invention and its stack bus bar insulated rubber film of preparation
Can, resistance to environmental testing it is up to standard, fire resistance reaches UL94VTM-0 grade, with excellent high/low temperature peel strength, good adds
Work performance.
Prior art is compared, and the present invention has the advantages that：
A small amount of phenolic resin is added in halogen-free resin composition of the invention, virtue can be introduced in halogen-free resin composition
Ring, improves heat resistance and fire resistance.Phenolic resin and saturated polyester resin all contain hydroxyl simultaneously, all can be solid with isocyanates
Agent crosslinks curing reaction, so as to form interpenetrating polymer networks, the solidification objects system for obtaining has excellent heat resistance
With high temperature bonding performance.The anti-flammability of the stack bus bar insulated rubber film prepared using the halogen-free resin composition is reachable
UL94VTM-0 grades, and with excellent high temperature peel strength, processing characteristics and high/low-temperature impact performance, more high workload can be met
The application requirement of temperature stack bus bar.Using halogen-free flame retardants, increasingly strict environmental requirement can be met.
More than, only presently preferred embodiments of the present invention, for the person of ordinary skill of the art, can be according to this hair
Bright technical scheme and technology design makes other various corresponding changes and deformation, and all these changes and deformation should all belong to
In the scope of the claims in the present invention.
The present invention illustrates method detailed of the invention by above-described embodiment, but the invention is not limited in above-mentioned detailed
Method, that is, do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should
Understand, any improvement in the present invention, to addition, the concrete mode of the equivalence replacement and auxiliary element of each raw material of product of the present invention
Selection etc., all fall within protection scope of the present invention and it is open within the scope of.
Claims (19)
1. a kind of halogen-free resin composition, it is characterised in that according to mass fraction meter, the halogen-free resin composition includes as follows
Component：
2. halogen-free resin composition as claimed in claim 1, it is characterised in that the saturated polyester resin includes saturated polyester
In Resin A or saturated polyester resin B any one or both mixture；According to mass fraction meter, the saturated polyester tree
The addition of fat A is 0~30 part, and the addition of the saturated polyester resin B is 40~80 parts.
3. halogen-free resin composition as claimed in claim 1, it is characterised in that the molecular weight of the saturated polyester resin A exists
Between 3000~30000, between -30~65 DEG C, hydroxyl value is between 2~15mgKOH/g for glass transition temperature；The saturation
The molecular weight of polyester resin B between 5000~30000, glass transition temperature between 10~110 DEG C, hydroxyl value 2~
Between 15mgKOH/g.
4. halogen-free resin composition as claimed in claim 1, it is characterised in that the phenolic resin may be selected from thermosetting phenolic
The mixture of any one or two kinds in resin or thermoplastic phenolic resin.
5. flame resistance resin composite as claimed in claim 1, it is characterised in that the phenolic resin may be selected from bisphenol A-type
Phenolic resin, o-cresol-formaldehyde resin, phenol novolacs, aralkyl phenolic resin, promise volt clarke type phenolic resin, knot containing triazine
In the phenolic resin of structure any one or at least two mixture.
6. halogen-free resin composition as claimed in claim 1, it is characterised in that the curing agent is selected from aliphatic isocyanates
In curing agent, alicyclic isocyanate curing agent, aromatic isocyanate curing agent any one or at least two mixing
Thing；The aliphatic isocyanates curing agent is selected from appointing in hexamethylene diisocyanate dimer, tripolymer or addition product
Meaning it is a kind of or at least two mixtures；The alicyclic isocyanate curing agent is selected from dimerisation ispohorone diisolyanate
In body, tripolymer or addition product any one or at least two mixture；Described aromatic isocyanate curing agent choosing
From toluene diisocyanate dimer, tripolymer or addition product, 2,4- methyl diphenylene diisocyanate dimers, tripolymer or
Addition product, in XDI dimer, tripolymer or addition product any one or at least two mixing
Thing.
7. flame resistance resin composite as claimed in claim 1, it is characterised in that it is different that the curing agent is selected from room temperature reaction type
One or both of cyanate curing agent, Blocked Isocyanate Curing Agents mixture；The blocked isocyanate solidification
Agent needs high temperature just to possess reactivity after unsealing, and described deblocking temperature is less than 140 DEG C.
8. halogen-free resin composition as claimed in claim 1, it is characterised in that the halogen-free flame retardants can be phosphor-containing flame-proof
Agent, nitrogenous flame ratardant or the two combination.
9. halogen-free resin composition as claimed in claim 8, it is characterised in that the phosphonium flame retardant be selected from SPB-100,
In OP-930, OP-935, SP-703H any one or at least two mixture.
10. halogen-free resin composition as claimed in claim 8, it is characterised in that the nitrogenous flame ratardant be melamine and
Its salt.
11. halogen-free resin compositions as claimed in claim 1, it is characterised in that also including filler, as mass fraction, institute
Filler is stated for 0~100 part, described filler is aluminium hydroxide, magnesium hydroxide, silica, magnesia, zeolite, wollastonite, viscous
In soil, talcum, mica, calcium carbonate and calcium silicates any one or at least two mixture.
12. halogen-free resin compositions as claimed in claim 1, it is characterised in that also including antioxidant, according to mass fraction
Meter, the addition of the antioxidant is 0.01~1 part, the antioxidant be Hinered phenols antioxidant 1010,1076,1098,
2246 and phosphite ester kind antioxidant 168,618 in any one or at least two mixture.
13. halogen-free resin compositions as claimed in claim 1, it is characterised in that also including coupling agent, according to mass fraction
Meter, the addition of the coupling agent is 0.01~5 part, and the coupling agent is any in silane coupler, titanate coupling agent
One or two mixture, the silane coupler be KH171, KH151, KH172, KH792, KH550, KH560, KH570,
In KH530 any one or at least two mixture；The titanate coupling agent is TMC-101, TMC-102, TMC-
201st, in TMC-105, TMC-311w, TMC-311, TMC-2 any one or at least two mixture.
14. a kind of burning-resistant type adhesives, it is characterised in that including the Halogen resin group as described in any one of claim 1~13
Compound and organic solvent, the solid content of the burning-resistant type adhesive is 20wt%~60wt%.
15. burning-resistant type adhesives as claimed in claim 14, it is characterised in that the organic solvent is butanone, acetone, hexamethylene
It is any in ketone, toluene, dimethylbenzene, glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate
It is a kind of or at least two mixture.
16. a kind of stack bus bar insulated rubber films, it is characterised in that be coated on including insulation film and single or double described exhausted
The gluing oxidant layer that the burning-resistant type adhesive as described in any one of claim 14~15 on edge film is formed.
17. stack bus bar insulated rubber films as claimed in claim 16, it is characterised in that the insulation film is for poly- to benzene two
Formic acid glycol ester film, polybutylene terephthalate (PBT) film, PEN film, Kapton
Or poly film.
18. stack bus bar insulated rubber films as claimed in claim 16, it is characterised in that the thickness of the insulation film is
100~250 μm；The thickness of the gluing oxidant layer is 10~50 μm.
A kind of 19. methods of the stack bus bar insulated rubber film prepared as described in any one of claim 16~18, its feature exists
In, including step：
(1) saturated polyester resin, phenolic resin, curing agent and halogen-free flame retardants are weighed according to the mass fraction, it is molten with organic
Agent is mixed to prepare burning-resistant type adhesive；And
(2) the burning-resistant type adhesive single or double is coated on insulating substrate, feeding baking oven is described organic molten to remove
Agent, forms the gluing oxidant layer of solid-state, and winding obtains the stack bus bar insulated rubber film.
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|---|---|---|---|
| CN201611246829.5A CN106700428A (en) | 2016-12-29 | 2016-12-29 | Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246829.5A CN106700428A (en) | 2016-12-29 | 2016-12-29 | Halogen-free resin composition, adhesive and laminated busbar insulating adhesive film prepared therefrom, and preparation method of insulating adhesive film |
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| CN108587508A (en) * | 2018-03-29 | 2018-09-28 | 广东莱尔新材料科技股份有限公司 | A kind of hot melt adhesive film and preparation method thereof of high viscous metal power |
| CN109666445A (en) * | 2018-12-27 | 2019-04-23 | 广东生益科技股份有限公司 | A kind of resin combination includes its stack bus bar insulated rubber film and preparation method thereof |
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| CN102690494A (en) * | 2012-06-08 | 2012-09-26 | 中国石油化工股份有限公司 | Phenolic resin composition and foaming material prepared from same |
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Application publication date: 20170524 |