CN106674916A - Flame-retardant resin composition, adhesive prepared from flame-retardant resin composition, insulation adhesive film used for laminated busbar, and preparation method of insulation adhesive film - Google Patents
Flame-retardant resin composition, adhesive prepared from flame-retardant resin composition, insulation adhesive film used for laminated busbar, and preparation method of insulation adhesive film Download PDFInfo
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- CN106674916A CN106674916A CN201611246785.6A CN201611246785A CN106674916A CN 106674916 A CN106674916 A CN 106674916A CN 201611246785 A CN201611246785 A CN 201611246785A CN 106674916 A CN106674916 A CN 106674916A
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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
- 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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
- C09J7/35—Heat-activated
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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
- 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
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention provides a flame-retardant resin composition, which comprises, by mass part, 40-110 parts of a saturated polyester resin, 5-40 parts of a phenolic resin, 1-20 parts of a curing agent, 10-100 parts of a fire retardant, 0.01-1 part of an anti-oxidant and 0.01-5 parts of a coupling agent. A small amount of phenolic resin is added in the flame-retardant resin composition, so that aromatic rings are introduced to the flame-retardant resin composition and thermal resistance and flame resistance of the flame-retardant resin composition are improved. Both of the phenolic resin and the saturated polyester resin contain hydroxyl groups, which react with the curing agent for a cross-linking curing reaction, so that interpenetrating polymer networks are formed and a condensate excellent in thermal resistance, flame retardance and high-temperature bonding performance is obtained. The invention further provides an adhesive prepared from the flame-retardant resin composition, an insulation adhesive film used for a laminated busbar, and a preparation method of the insulation adhesive film.
Description
Technical field
The present invention relates to stack bus bar insulated rubber film field, more particularly to a kind of flame resistance resin composite 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 can be regarded as distribution as a kind of row of the connection with multi-level composite construction, stack bus bar
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 high skill
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 used 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 insulant Jing hot pressing, typically using copper, aluminum as conductor material,
Then using insulated rubber film is as bonding and insulate between conductor material；As the insulating cement of bonding and insulant between conductor
Film, the quality of its performance has vital impact for the performance quality of stack bus bar.Currently, for the exhausted of stack bus bar
The adhesive of edge glued membrane mainly has epoxiess adhesive and saturated polyester class adhesive.Epoxiess 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 short phase, pressing time length, the shortcomings of 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 length, pressing time are 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
Add the mode of a small amount of firming agent so as to form interpenetrating polymer networks structure or produce 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.
Therefore, it is necessary to provide a kind of flame resistance resin composite, the adhesive containing the flame resistance resin composite, adopt
The stack bus bar insulated rubber film made of the flame resistance resin composite, its good flame retardation effect is peeled off with excellent high temperature
Intensity, processing characteristics and high/low-temperature impact performance, can meet the application requirement of more elevated operating temperature stack bus bar, existing to overcome
The deficiency of technology.
The content of the invention
An object of the present invention is to provide a kind of flame resistance resin composite；The second object of the present invention is to provide
A kind of adhesive made using above-mentioned flame resistance resin composite；The third object of the present invention is to provide a kind of using above-mentioned
The stack bus bar insulated rubber film that flame resistance resin composite makes；The fourth object of the present invention is to provide described lamination mother
The preparation method of row's insulated rubber film.Described stack bus bar adopts above-mentioned flame resistance resin composite with insulated rubber film, its resistance
Fuel efficiency fruit is good, with excellent high temperature peel strength, processing characteristics and high/low-temperature impact performance, can meet more elevated operating temperature and fold
The application requirement of layer busbar.
To realize the purpose, the present invention provides a kind of flame resistance resin composite, according to mass fraction meter, the flame retardant type
Resin combination 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 parts, 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 parts, 35 parts or 39 parts；, 1~20 part of firming agent, for example, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 19 parts；And fire retardant 10
~100 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.
The flame resistance resin composite of the present invention, as matrix resin, is coordinated phenolic resin, is consolidated using saturated polyester resin
Agent and fire retardant are constituted, and wherein phenolic resin has good anti-flammability and an excellent thermostability, and saturated polyester resin and
Contain hydroxyl in phenolic resin, all can react with firming agent, formed interpenetrating polymer networks, so as to get solidification objects system tool
There is 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, firming 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 mixture；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, 15mgKOH/g；The saturated polyester resin B's divides
Son amount Mn between 5000~30000, glass transition temperature Tg between 10~110 DEG C, for example：10℃、15℃、20℃、
30 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C or 110 DEG C；Hydroxyl value between 2~15mgKOH/g, such as 2mgKOH/
g、5mgKOH/g、10mgKOH/g、15mgKOH/g。
According to mass fraction meter, the addition of the saturated polyester resin A is 0~30 part, can be 1 part, 5 parts, 10 parts,
20 parts, 25 parts or 30 parts；The addition of the saturated polyester resin B is 40~80 parts, can be 40 parts, 50 parts, 60 parts, 70 parts
Or 80 parts.
The saturated polyester resin A can preferably SK Chemical of Korea manufacture ES450, ES850, ES750, also Germany
S1611, S1426, S1313 of the manufacture of Evonik companies etc.；Described saturated polyester resin B preferably Germany's Evonik company systems
ES901, ES600, ES120 of L952, L912 for making etc., also SK Chemical of Korea manufacture etc..
It is preferred that the phenolic resin may be selected from any one in thermosetting phenolic resin or thermoplastic phenolic resin 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
Phenolic resin, aralkyl phenolic resin, promise volt clarke type phenolic resin, in the phenolic resin containing triazine structure any one or
At least two mixture.
It is preferred that pressing structure choice, the firming agent is solid selected from aliphatic isocyanates firming agent, alicyclic isocyanate
In agent, aromatic isocyanate firming agent any one or at least two mixture；The aliphatic isocyanates are consolidated
Agent in hexamethylene diisocyanate (HDI) dimer, trimer or the addition product any one or at least two
Mixture；The alicyclic isocyanate firming agent is selected from isophorone diisocyanate (IPDI) dimer, trimer or adds
Into any one in thing or at least two mixture；Described aromatic isocyanate firming agent is selected from toluene diisocynate
Ester (TDI) dimer, trimer or addition product, 2,4- methyl diphenylene diisocyanates (MDI) dimer, trimer or addition
Thing, in XDI (XDI) dimer, trimer or addition product any one or at least two mixing
Thing.
It is preferred that selecting by response characteristic, the firming agent is different selected from room temperature reaction type isocyanate curing agent, enclosed type
Cyanate firming agent；The Blocked Isocyanate Curing Agents need just possess reactivity, described deblocking after high temperature deblocking
Temperature is less than 140 DEG C.Deblocking temperature is too high, causes baking and pressing-in temp too high, brings energy consumption to rise, and high temperature long-time is pressed
Close, can also cause thin polymer film hydraulic performance decline.
It is preferred that the fire retardant is including any one in halogenated flame retardant, halogen system fire retarding synergist, metal hydroxidess
Kind or at least two mixture；The halogenated flame retardant be TDE, brominated styrene, brominated epoxy resin, four
In the double tetrabromo phthalimide of bromine bisphenol-A, HBCD, ethylene any one or at least two mixture；
The halogen system fire retarding synergist is the mixture of any one in antimony oxide, antimony pentoxide or two kinds；The metal
Hydroxide is the mixture of any one in magnesium hydroxide, aluminium hydroxide or two kinds.
It is preferred that the flame resistance resin composite also includes antioxidant, according to mass fraction meter, the antioxidant adds
Dosage is 0.01~1 part.Stack bus bar insulated rubber film service life can be extended, adhesive aging mistake when slowing down or suppress hot pressing
The carrying out of journey, in the present invention Hinered phenols antioxidant 1010,1076,1098,2246 and phosphorous acid esters antioxygen are preferably used
Agent 168,618.
It is preferred that the flame resistance resin composite also includes coupling agent, according to mass fraction meter, the coupling agent adds
Dosage is 0.01~5 part, and the coupling agent is the mixing of any one in silane coupler, titanate coupling agent or two kinds
Thing, the silane coupler is any one in KH171, KH151, KH172, KH792, KH550, KH560, KH570, KH530
Kind or at least two mixture；The titanate coupling agent is TMC-101, TMC-102, TMC-201, TMC-105, TMC-
In 311w, TMC-311, TMC-2 any one or at least two mixture.
The present invention also provides a kind of burning-resistant type adhesive, including flame resistance resin composite as above and organic molten
Agent, the solid content of the burning-resistant type adhesive is 30wt%~60wt%, can obtain suitable viscosity, there is provided good processing
Property, it is ensured that to use and occur without visual defects during (as coated).
It is preferred that the organic solvent is butanone, acetone, Ketohexamethylene, toluene, dimethylbenzene, glycol monoethyl ether, Propylene Glycol
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 above on insulation film is formed.
It is preferred that the insulation film is pet film (PET), polybutylene terephthalate
Ester film (PBT), PEN thin film (PEN), Kapton (PI) or poly- isophthaloyl isophthalic two
Amine thin film (NOMEX).
It is preferred that the thickness of the insulation film is 100~250 μm；For example：100μm、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 250 μm.
The thickness of the gluing oxidant layer is 10~50 μm.For example：10 μm, 20 μm, 30 μm, 40 μm or 50 μm.
The present invention also provides a kind of method for preparing stack bus bar insulated rubber film as above, it is characterised in that bag
Include step：
(1) saturated polyester resin, phenolic resin, firming agent, fire retardant, antioxidant and idol are weighed according to the mass fraction
Connection agent, is simultaneously mixed it with organic solvent with the use of high shear dispersed with stirring equipment using ball mill, jar mill or sand mill
Close, 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, Ketohexamethylene, toluene, dimethylbenzene, glycol monoethyl ether, Propylene Glycol
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：
Add a small amount of phenolic resin in the flame resistance resin composite of the present invention, can draw in flame resistance resin composite
Enter aromatic ring, improve thermostability and fire resistance.Simultaneously phenolic resin and saturated polyester resin all contain hydroxyl, all can be with firming agent
Curing reaction is crosslinked, so as to form interpenetrating polymer networks, the solidification objects system for obtaining has excellent anti-flammability, heat-resisting
Property and high temperature bonding performance.The anti-flammability of the stack bus bar insulated rubber film prepared using the flame resistance resin composite is reachable
UL94VTM-0 levels, 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.
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 flame resistance resin composite, including the weight portions of saturated polyester resin B (L952) 40 calculated in parts by weight,
The weight portion of thermoplastic phenolic resin 5, the weight portion of aliphatic isocyanates firming agent 5, the weight portion of antimony oxide 10, decabrominated dipheny
The weight portion of ethane 20, the weight portion of aluminium hydroxide 10, the weight portion of antioxidant (1010) 0.2, the weight portion of coupling agent (KH560) 0.09.
Described flame resistance resin composite is applied to into stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted by described with butanone
Saturated polyester resin B, thermoplastic phenolic resin, aliphatic isocyanates firming agent, antimony oxide, TDE, hydrogen
Aluminium oxide, antioxidant, the liquid dispersion (solids content 35%) of coupling agent composition, are blended into burning-resistant type adhesive.
As shown in figure 1, again the burning-resistant type adhesive coating machine one side is coated in into the PET insulation films that thickness is 100 μm
On 10, rubberization thickness is 15 μm；
Then process 5 minutes at 100 DEG C, so that butanone volatilization, forms the gluing oxidant layer of solid-state on PET dielectric films
20；
Finally wind the stack bus bar insulated rubber film 1 for obtaining the flame resistance resin composite.
Embodiment 2
A kind of flame resistance resin composite, including the weight of saturated polyester resin A (ES450) 22 calculated in parts by weight
Part, the weight portions of saturated polyester resin B (ES901) 53, the weight portion of thermosetting phenolic resin 15, aromatic isocyanate firming agent 10
Weight portion, the weight portion of antimony pentoxide 10, the weight portion of HBCD 18, the weight portion of magnesium hydroxide 9, antioxidant (168)
0.15 weight portion, the weight portion of coupling agent (KH530) 0.2.
Described flame resistance resin composite is applied to into stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted by institute with Ketohexamethylene
State saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aromatic isocyanate firming agent, antimony pentoxide,
HBCD, magnesium hydroxide, antioxidant, the liquid dispersion (solids content 50%) of coupling agent composition, are blended into fire-retardant
Type adhesive.
As shown in Fig. 2 being coated in the PET insulation films that thickness is 100 μm by the burning-resistant type adhesive coating machine is two-sided again
On 10 ', rubberization thickness is 15 μm；
Then process 5 minutes at 160 DEG C, so that Ketohexamethylene volatilization, forms the gluing oxidant layer of solid-state on PET dielectric films
20’；
Finally wind the stack bus bar insulated rubber film 1 ' for obtaining the flame resistance resin composite.
Embodiment 3
A kind of flame resistance resin composite, including the weight portions of saturated polyester resin A (S1611) 30 for calculating by weight,
The weight portions of saturated polyester resin B (ES600) 75, the weight portion of thermoplastic phenolic resin 35, the weight of alicyclic isocyanate firming agent 8
Part, the double weight portion of tetrabromo phthalimide 38 of the weight portion of antimony oxide 13, ethylene, the weight portion of antioxidant (168) 0.1,
The weight portion of coupling agent (KH172) 0.5.
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First with ethyl acetate adjust by
The saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, alicyclic isocyanate firming agent, three oxidations two
The double tetrabromo phthalimides of antimony, ethylene, antioxidant, the liquid dispersion (solids content is 55%) of coupling agent composition, mix
Make burning-resistant type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PEN insulation films that thickness is 150 μm again, rubberization thickness
For 40 μm；
Then process 5 minutes at 120 DEG C, so that ethyl acetate volatilization, forms the adhesive of solid-state on PEN dielectric films
Layer；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 4
A kind of flame resistance resin composite, it is poly- including 8 parts of the saturated polyester resin A (ES450), saturation for calculating by weight
47 parts of ester resin B (L952), 8 parts of thermosetting phenolic resin, 5 parts of aliphatic isocyanates firming agent, 7 parts of antimony oxide, bromine
Change 15 parts of styrene, 5 parts of aluminium hydroxide, (1076) 0.9 parts of antioxidant, 0.07 part of coupling agent (KH171).
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted by described with butanone
Saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aliphatic isocyanates firming agent, antimony oxide, bromine
Change styrene, aluminium hydroxide, antioxidant, the liquid dispersion (solids content is 60%) of coupling agent composition, be blended into flame retardant type
Adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PI insulation films that thickness is 110 μm again, rubberization thickness
For 12 μm；
Then process 9 minutes at 110 DEG C, so that butanone volatilization, forms the gluing oxidant layer of solid-state on PI dielectric films；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 5
A kind of flame resistance resin composite, including 11 parts of the saturated polyester resin A (ES850), the saturation that calculate by weight
68 parts of polyester resin B (L912), 14 parts of thermoplastic phenolic resin, 8 parts of alicyclic isocyanate firming agent, antimony pentoxide 14
Part, 30 parts of brominated epoxy resin, 10 parts of magnesium hydroxide, (1098) 0.4 parts of antioxidant, 3.8 parts of coupling agent (KH151).
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted by described with acetone
Saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, alicyclic isocyanate firming agent, antimony pentoxide, bromine
Change epoxy resin, magnesium hydroxide, antioxidant, the liquid dispersion (solids content is 45%) of coupling agent composition, be blended into fire-retardant
Type adhesive.
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 for 17 μm；
Then process 7 minutes at 165 DEG C, so that acetone volatilization, forms the adhesive of solid-state on NOMEX dielectric films
Layer；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 6
A kind of flame resistance resin composite, including 29 parts of the saturated polyester resin A (ES750), the saturation that calculate by weight
72 parts of polyester resin B (ES901), 19 parts of thermosetting phenolic resin, 19 parts of aromatic isocyanate firming agent, antimony oxide 12
Part, 42 parts of HBCD, 12 parts of aluminium hydroxide, (618) 1 parts of antioxidant, 2.6 parts of coupling agent (KH172).
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted by described with toluene
Saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aromatic isocyanate firming agent, antimony oxide, six
Bromine cyclododecane, aluminium hydroxide, antioxidant, the liquid dispersion (solids content is 57%) of coupling agent composition, are blended into fire-retardant
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
For 20 μm；
Then process 6 minutes at 150 DEG C, so that toluene volatilization, forms the gluing oxidant layer of solid-state on PET dielectric films；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 7
A kind of flame resistance resin composite, including 17 parts of the saturated polyester resin A (S1611), the saturation that calculate by weight
59 parts of polyester resin B (ES600), 24 parts of thermoplastic phenolic resin, 11 parts of aliphatic isocyanates firming agent, antimony oxide 9
Part, 10 parts of antimony pentoxide, 35 parts of TDE, 8 parts of aluminium hydroxide, 3 parts of magnesium hydroxide, (1010) 0.5 parts of antioxidant,
4.7 parts of coupling agent (KH792).
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted by institute with dimethylbenzene
State saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, aliphatic isocyanates firming agent, antimony oxide,
Antimony pentoxide, TDE, aluminium hydroxide, magnesium hydroxide, antioxidant, the liquid dispersion (solid of coupling agent composition
Content is 53%), to be blended into burning-resistant type adhesive.
The burning-resistant type adhesive coating machine one side is coated on the PBT insulation films that thickness is 140 μm again, rubberization thickness
For 31 μm；
Then process 7 minutes at 140 DEG C, so that dimethylbenzene volatilization, forms the adhesive of solid-state on PBT dielectric films
Layer；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 8
A kind of flame resistance resin composite, including 22 parts of the saturated polyester resin A (S1426), the saturation that calculate by weight
70 parts of polyester resin B (ES120), 33 parts of thermosetting phenolic resin, 15 parts of alicyclic isocyanate firming agent, antimony oxide 11
Part, 12 parts of antimony pentoxide, 50 parts of brominated styrene, 13 parts of aluminium hydroxide, (1076) 0.7 parts of antioxidant, coupling agent (KH550)
3.1 part.
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First spent glycol monomethyl ether is adjusted
Section is by the saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, alicyclic isocyanate firming agent, three oxygen
Change two antimony, antimony pentoxide, brominated styrene, aluminium hydroxide, antioxidant, the liquid dispersion (solids content of coupling agent composition
41%), to be blended into burning-resistant 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
For 38 μm；
Then process 6 minutes at 130 DEG C, so that glycol monoethyl ether volatilization, forms the glue of solid-state on PEN dielectric films
Adhesive layer；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 9
A kind of flame resistance resin composite, including 14 parts of the saturated polyester resin A (S1313), the saturation that calculate by weight
63 parts of polyester resin B (L952), 28 parts of thermoplastic phenolic resin, 13 parts of aromatic isocyanate firming agent, antimony oxide 31
Part, 57 parts of brominated epoxy resin, 8 parts of aluminium hydroxide, 1 part of magnesium hydroxide, (1098) 0.2 parts of antioxidant, coupling agent (KH560)
1.4 part.
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First adjusted with propylene glycol monomethyl ether
Section is by the saturated polyester resin A, saturated polyester resin B, thermoplastic phenolic resin, aromatic isocyanate firming agent, three oxygen
Change two antimony, brominated epoxy resin, aluminium hydroxide, magnesium hydroxide, antioxidant, the liquid dispersion (solids content of coupling agent composition
37%), to be blended into burning-resistant 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
For 42 μm；
Then process 4 minutes at 140 DEG C, so that propylene glycol monomethyl ether volatilization, forms the glue of solid-state on PI dielectric films
Adhesive layer；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Embodiment 10
A kind of flame resistance resin composite, including 27 parts of the saturated polyester resin A (ES450), the saturation that calculate by weight
78 parts of polyester resin B (ES901), 39 parts of thermosetting phenolic resin, 17 parts of aliphatic isocyanates firming agent, antimony oxide 28
Part, 24 parts of brominated styrene, 26 parts of brominated epoxy resin, 11 parts of aluminium hydroxide, (2246) 0.6 parts of antioxidant, coupling agent
(KH530) 0.03 part.
By the flame resistance resin composite for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing flame resistance resin composite：First use propylene glycol monomethyl ether vinegar
Acid esters is adjusted by the saturated polyester resin A, saturated polyester resin B, thermosetting phenolic resin, aliphatic isocyanates solidification
Agent, antimony oxide, brominated styrene, brominated epoxy resin, aluminium hydroxide, antioxidant, the liquid dispersion of coupling agent composition
(solids content is 32%), is blended into 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 for 47 μm；
Then process 3 minutes at 150 DEG C, so that propylene glycol monomethyl ether acetate volatilization, forms on NOMEX dielectric films
The gluing oxidant layer of solid-state；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Comparative example 1
A kind of flame resistance resin composite, by the weight portions of saturated polyester resin A (S1313) 20 for calculating by weight, satisfies
With the weight portions of polyester resin B (L912) 60, the weight portion of aromatic isocyanate firming agent 10, the weight portion of antimony oxide 12, bromine
Change the weight portion of styrene 30, the weight portion of antioxidant (1010) 0.2, the weight portion butanone of coupling agent (KH570) 0.3 be adjusted to (Gu
Body content is liquid dispersion 43%).
The flame resistance resin composite coating machine one side is coated on the PET insulation films that thickness is 150 μm again, gluing
Thickness is 30 μm；
Then process 5 minutes at 90 DEG C, so that solvent volatilization, forms solid-state composition nitride layer on PET insulation films；
Finally wind the stack bus bar insulated rubber film for obtaining the flame resistance resin composite.
Comparative example 2
The weight portions of saturated polyester resin A (ES450) 15, the weight portions of saturated polyester B (L952) 67, the heat for calculating by weight
The weight portion of plastic phenolic resin 20, the weight portion of antimony pentoxide 18, the weight portion of tetrabromobisphenol A 30, the weight of antioxidant (168) 0.2
Part, the weight portion butanone of coupling agent (KH172) 0.2 are adjusted to the liquid dispersion of (solids content 50%).
The resin combination coating machine one side is coated on the PET insulation films that thickness is 125 μm again, rubberization thickness is
35μm；
Then process 3 minutes at 110 DEG C, so that solvent volatilization, forms solid-state composition nitride layer on PET insulation films；
Finally wind the stack bus bar insulated rubber film for obtaining the resin combination.
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.
Performance test is carried out with insulated rubber film to the stack bus bar of embodiment 1~10, comparative example 1~3 and existing product, 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 measure 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, cold shock testing is then carried out.Cold shock testing condition is：-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, and 125 DEG C/constant temperature 0.5 is little
When, 125 DEG C are cooled to -40 DEG C/1 minute, the circulation about 1 hour of the above one.
After thermal shock between glued membrane and copper bar without foaming, without cracking then for qualified, it is otherwise unqualified.
(6) hydrothermal aging performance
By insulated rubber film and copper bar high-temperature laminating, hydrothermal aging test 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
Determine according to the vertical combustions of UL 94.
Concrete test result is as shown in table 1 below.
From table 1 it follows that not adding phenolic resin respectively in comparative example 1 and comparative example 2 and firming agent is changed
Property, it is impossible to the aromatic ring in phenolic resin is effectively introduced in resin combination, three-dimensional crosslinked network is formed, therefore using the resin group
The high temperature peel strength of insulated rubber film prepared by compound is substantially less than embodiment.Comparative example 3 adopts Chinese patent
The embodiment of CN104178044A, because epoxy resin open loop and isocyanate curing agent reaction temperature are generally more than 200 DEG C,
Therefore at a lower temperature epoxy resin cannot carry out effective cross-linking reaction, cause to add epoxy resin to improving saturated polyester
Thermostability effect is very limited, and prepared insulated rubber film can only meet the application requirement of 105 DEG C of stack bus bars, high at 125 DEG C
It is unqualified in temperature test and high/low-temperature impact circulation.And phenolic resin is with the addition of in the flame resistance resin composite of embodiment
Modified, phenolic resin can react to form three-dimensional crosslinked network at a lower temperature with isocyanate curing agent and saturated polyester,
The aromatic ring of phenolic resin is introduced in the curing system of flame resistance resin composite, so the punching of its high temperature bonding performance, high/low temperature
Hit performance, hydrothermal aging performance to be greatly improved both with respect to comparative example, in 125 DEG C of environment peel strength still greater than 1.0N/mm,
Hydrothermal aging 1000 hours, high-temperature baking 240 are little under 200 high/low-temperature impact circulations of experience, 85 DEG C and 85% damp condition
Shi Hou, cracking not yet, foaming phenomena.With phenolic resin modified saturated polyester resin, phenolic resin and saturated polyester resin
In contain hydroxyl, and all can crosslink reaction with isocyanate curing agent, form interpenetrating polymer networks, be remarkably improved
The thermostability and high temperature peel strength of saturated polyester adhesive.
In sum, the electrical resistance of flame resistance resin composite 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 levels, with excellent high/low temperature peel strength, it is good plus
Work performance.
Prior art is compared, and the present invention has the advantages that：
Add a small amount of phenolic resin in the flame resistance resin composite of the present invention, can draw in flame resistance resin composite
Enter aromatic ring, improve thermostability and fire resistance.Simultaneously phenolic resin and saturated polyester resin all contain hydroxyl, all can be with firming agent
Curing reaction is crosslinked, so as to form interpenetrating polymer networks, the solidification objects system for obtaining has excellent thermostability and height
Warm adhesive property.The anti-flammability of the stack bus bar insulated rubber film prepared using the flame resistance resin composite is up to UL94VTM-
0 grade, and with excellent high temperature peel strength, processing characteristics and high/low-temperature impact performance, more elevated operating temperature lamination can be met
The application requirement of busbar.
More than, only presently preferred embodiments of the present invention, for the person of ordinary skill of the art, can be according to this
Bright technical scheme and technology design makes other various corresponding changes and deformation, and all these changes and deformation all should belong to
In the scope of the claims in the present invention.
The present invention illustrates the method detailed of the present 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, addition, the concrete mode of equivalence replacement and auxiliary element to 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 (15)
1. a kind of flame resistance resin composite, it is characterised in that according to mass fraction meter, the flame resistance resin composite includes
Following component：
2. flame resistance resin composite as claimed in claim 1, it is characterised in that the saturated polyester resin is poly- including saturation
The mixture of any one in ester Resin A or saturated polyester resin B or both；According to mass fraction meter, the saturated polyester
The addition of Resin A is 0~30 part, and the addition of the saturated polyester resin B is 40~80 parts；The saturated polyester resin A
Molecular weight between 3000~30000, glass transition temperature between -30~65 DEG C, hydroxyl value 2~15mgKOH/g it
Between；The molecular weight of the saturated polyester resin B between 5000~30000, glass transition temperature between 10~110 DEG C,
Hydroxyl value is between 2~15mgKOH/g.
3. flame resistance resin composite as claimed in claim 1, it is characterised in that the phenolic resin may be selected from thermosetting phenol
The mixture of any one or two kinds in urea formaldehyde or thermoplastic phenolic resin.
4. 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 lie prostrate clarke type phenolic resin, tie containing triazine
In the phenolic resin of structure any one or at least two mixture.
5. flame resistance resin composite as claimed in claim 1, it is characterised in that the firming agent is selected from aliphatic Carbimide.
In ester firming agent, alicyclic isocyanate firming agent, aromatic isocyanate firming agent any one or at least two it is mixed
Compound；The aliphatic isocyanates firming agent is in hexamethylene diisocyanate dimer, trimer or addition product
Any one or at least two mixture；The alicyclic isocyanate firming agent is selected from dimerisation ispohorone diisolyanate
In body, trimer or addition product any one or at least two mixture；Described aromatic isocyanate firming agent choosing
From toluene diisocyanate dimer, trimer or addition product, 2,4- methyl diphenylene diisocyanate dimers, trimer or
Addition product, in XDI dimer, trimer or addition product any one or at least two mixing
Thing.
6. flame resistance resin composite as claimed in claim 1, it is characterised in that the firming agent is different selected from room temperature reaction type
One or both of cyanate firming agent, Blocked Isocyanate Curing Agents mixture；The blocked isocyanate solidification
Agent needs just possess reactivity after high temperature deblocking, and described deblocking temperature is less than 140 DEG C.
7. flame resistance resin composite as claimed in claim 1, it is characterised in that the fire retardant include halogenated flame retardant,
In halogen system fire retarding synergist, metal hydroxidess any one or at least two mixture；The halogenated flame retardant is ten
The double tetrabromo-phthalic diformazans of bromine diphenylethane, brominated styrene, brominated epoxy resin, tetrabromobisphenol A, HBCD, ethylene
In acid imide any one or at least two mixture；The halogen system fire retarding synergist is antimony oxide, five oxidations two
The mixture of any one or two kinds in antimony；The metal hydroxidess are any one in magnesium hydroxide, aluminium hydroxide
Or two kinds of mixture.
8. flame resistance resin composite 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.
9. flame resistance resin composite 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.
10. a kind of burning-resistant type adhesive, it is characterised in that include the flame-retardant resin group as described in any one of claim 1~9
Compound and organic solvent, the solid content of the burning-resistant type adhesive is 30wt%~60wt%.
11. burning-resistant type adhesives as claimed in claim 10, 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.
12. 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 10~11 of edge film surface is formed.
13. stack bus bar insulated rubber films as claimed in claim 12, it is characterised in that the insulation film is for poly- to benzene two
Formic acid glycol ester thin film, polybutylene terephthalate (PBT) thin film, PEN thin film, Kapton
Or poly(isophthaloyl metaphenylene diamine) thin film.
14. stack bus bar insulated rubber films as claimed in claim 12, 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 15. methods of the stack bus bar insulated rubber film prepared as described in any one of claim 12~14, its feature exists
In, including step：
(1) saturated polyester resin, phenolic resin, firming agent and fire retardant are weighed according to the mass fraction, it is mixed with organic solvent
Close and burning-resistant type adhesive is obtained；And
(2) the burning-resistant type adhesive single or double is coated on into insulating substrate surface, sends into baking oven described organic to remove
Solvent, forms the gluing oxidant layer of solid-state, and winding obtains the stack bus bar insulated rubber film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246785.6A CN106674916A (en) | 2016-12-29 | 2016-12-29 | Flame-retardant resin composition, adhesive prepared from flame-retardant resin composition, insulation adhesive film used for laminated busbar, and preparation method of insulation adhesive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611246785.6A CN106674916A (en) | 2016-12-29 | 2016-12-29 | Flame-retardant resin composition, adhesive prepared from flame-retardant resin composition, insulation adhesive film used for laminated busbar, and preparation method of insulation adhesive film |
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| Publication Number | Publication Date |
|---|---|
| CN106674916A true CN106674916A (en) | 2017-05-17 |
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| CN201611246785.6A Pending CN106674916A (en) | 2016-12-29 | 2016-12-29 | Flame-retardant resin composition, adhesive prepared from flame-retardant resin composition, insulation adhesive film used for laminated busbar, and preparation method of insulation adhesive film |
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| CN107954612A (en) * | 2017-12-04 | 2018-04-24 | 滕州市耀海玻雕有限公司 | A kind of manufacturing process of vacuum glass |
| CN108084902A (en) * | 2017-12-19 | 2018-05-29 | 广东莱尔新材料科技股份有限公司 | A kind of viscous metal power is high, the Halogen hot melt adhesive film of good flame resistance and preparation method thereof |
| CN112877018A (en) * | 2021-03-30 | 2021-06-01 | 东莞市安派电子有限公司 | Formula of lithium battery side plate adhesive |
| CN112877006A (en) * | 2021-01-11 | 2021-06-01 | 苏州赛伍应用技术股份有限公司 | Hot-pressing insulating film and flexible flat cable comprising same |
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| CN103214999A (en) * | 2012-01-18 | 2013-07-24 | 上海特镭宝材料科技有限公司 | Color-variable adhesive and adhesive tape |
| CN103937152A (en) * | 2014-04-11 | 2014-07-23 | 四川东材科技集团股份有限公司 | Polyester-phenolic aldehyde-epoxy composite material and preparation method thereof |
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| CN103214999A (en) * | 2012-01-18 | 2013-07-24 | 上海特镭宝材料科技有限公司 | Color-variable adhesive and adhesive tape |
| CN102757755A (en) * | 2012-07-17 | 2012-10-31 | 湖南高华环保股份有限公司 | Preparation method for high-temperature resistant, leak-proof and corrosion-resistant adhesive |
| CN103937152A (en) * | 2014-04-11 | 2014-07-23 | 四川东材科技集团股份有限公司 | Polyester-phenolic aldehyde-epoxy composite material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107954612A (en) * | 2017-12-04 | 2018-04-24 | 滕州市耀海玻雕有限公司 | A kind of manufacturing process of vacuum glass |
| CN107954612B (en) * | 2017-12-04 | 2020-08-28 | 滕州市耀海玻雕有限公司 | Manufacturing process of vacuum glass |
| CN108084902A (en) * | 2017-12-19 | 2018-05-29 | 广东莱尔新材料科技股份有限公司 | A kind of viscous metal power is high, the Halogen hot melt adhesive film of good flame resistance and preparation method thereof |
| CN112877006A (en) * | 2021-01-11 | 2021-06-01 | 苏州赛伍应用技术股份有限公司 | Hot-pressing insulating film and flexible flat cable comprising same |
| CN112877018A (en) * | 2021-03-30 | 2021-06-01 | 东莞市安派电子有限公司 | Formula of lithium battery side plate adhesive |
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Application publication date: 20170517 |