CN106700498A - Thermoplastic resin composition and adhesive prepared from same, insulation adhesive film used for laminated bus bar and preparation method of insulation adhesive film - Google Patents
Thermoplastic resin composition and adhesive prepared from same, insulation adhesive film used for laminated bus bar and preparation method of insulation adhesive film Download PDFInfo
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- CN106700498A CN106700498A CN201611244582.3A CN201611244582A CN106700498A CN 106700498 A CN106700498 A CN 106700498A CN 201611244582 A CN201611244582 A CN 201611244582A CN 106700498 A CN106700498 A CN 106700498A
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- 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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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- 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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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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- 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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- 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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Abstract
The invention provides a thermoplastic resin composition. The thermoplastic resin composition comprises the following components in parts by mass: 50-85 parts of thermoplastic polyurethane resin, 5-20 parts of saturated polyester resin, 0.5-8 parts of a compatilizer, 0.1-1 part of an antioxidant and 20-100 parts of a flame retardant, wherein the thermoplastic polyurethane resin has excellent flexibility and high and low temperature resistance; and the saturated polyester resin has low melting point, poor high temperature resistance, good aging property and excellent adhesive property with metal and an insulation film. The thermoplastic polyurethane resin and the saturated polyester resin are blended and modified, a small amount of the compatilizer is added, polymer alloy with excellent compatibility can be obtained, and the polymer alloy has good high and low temperature impact property, aging property and adhesive property. The resin composition does not contain a curing agent, has good high temperature liquidity and can meet low temperature lamination requirements. The invention also provides an adhesive made by adopting the thermoplastic resin composition, an insulation adhesive film used for a laminated bus bar 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 thermoplastic 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, laminated bus bars, composite copper bar, composite bus etc., English name
Laminated Busbar.It is mainly based upon electromagnetic theory, by copper bar not only wide but also thin and very thin insulating materials hot pressing
Integrally form, by opposite electric current in adjacent wires, its magnetic field is cancelled out each other, and can reduce stray inductance.As lamination
The insulated rubber film of bonding and insulating materials in busbar between conductor, safety and reliability of its performance quality for stack bus bar
There is vital influence.Insulated rubber film is main to be made up of insulation film with the adhesive for being coated in its surface.Currently, use
Epoxies adhesive and polyester-class adhesive are mainly in the adhesive of stack bus bar insulated rubber film.Epoxies adhesive is a class
Hot setting adhesive, has the advantages that good adhesive property, Good Heat-resistance, electrical insulation capability be good, dielectric properties are excellent, but
There is also the shortcomings of Storage period is short, pressing time is long, pressing-in temp is high so that its application in stack bus bar insulated rubber film
It is restricted.Saturated polyester class adhesive is an analog thermoplastic adhesive, although with storage time it is long, that pressing time is short etc. is excellent
Point, but the high temperature bonding performance of saturated polyester class adhesive is typically poor, it is also difficult to meet stack bus bar insulated rubber film
Application requirement.
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 is obtained with epoxide modified saturated polyester adhesive.But epoxy resin open loop is anti-with isocyanates
Temperature is answered usually above 200 DEG C, is difficult to form interpenetrating polymer networks structure to improve with saturated polyester resin under compared with low temperature
The high-temperature behavior of saturated polyester adhesive system；And epoxy resin modification is added in saturated polyester resin, modified adhesive may be caused
Stick becomes fragile, and storge quality declines.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.Addition curing agent makes saturated polyester resin forming part cross-linked network knot
Structure, no doubt can be improved the high temperature bonding performance of saturated polyester adhesive, but saturated polyester adhesive is before pressing
With regard to forming part cross-linked network structure, although overall to keep thermoplasticity, but it has formed certain three-dimensional net structure, does not have
Mobility and wellability under sharp melting point, high temperature are greatly reduced, and need to typically be pressed more than 150 DEG C could realize effectively gluing
Connect.Pressing-in temp is raised, and not only brings energy consumption to rise, and pressing will cause insulation film hydraulic performance decline for a long time under high temperature.
Additionally, as the structure of stack bus bar becomes to become increasingly complex, needing multiple high temp to press in many cases could be molded, too high
Pressing-in temp will cause the product qualified rate to reduce.
Therefore, how to realize on the premise of thermoplastic resin composition's high-temperature behavior is not reduced, reducing pressing-in temp, subtracting
Few pressing time is one of key issue urgently to be resolved hurrily in industry.
The content of the invention
An object of the present invention is to provide a kind of thermoplastic resin composition；The second object of the present invention is to provide
A kind of adhesive made using above-mentioned thermoplastic resin composition；The third object of the present invention is to provide a kind of using above-mentioned
The stack bus bar insulated rubber film that thermoplastic resin composition makes；The fourth object of the present invention is that the lamination described in offer is female
The preparation method of row's insulated rubber film.Described stack bus bar uses above-mentioned thermoplastic resin composition with insulated rubber film, its pressure
Close temperature low, with excellent high temperature peel strength, processing characteristics and high/low-temperature impact performance, low temperature pressing lamination can be met female
The application requirement of row.
To realize the purpose, the present invention provides a kind of thermoplastic resin composition, according to mass fraction meter, the thermoplasticity
Resin combination include 50~85 parts of TPU, for example, 51 parts, 52 parts, 55 parts, 58 parts, 60 parts, 65 parts, 70
Part, 75 parts, 80 parts；5~20 parts of saturated polyester resin, for example, 6 parts, 8 parts, 10 parts, 15 parts, 18 parts or 19 parts；Compatilizer 0.5
~8 parts, for example, 0.6 part, 1 part, 3 parts, 5 parts, 6 parts, 7 parts or 8 parts；And 20~100 parts of fire retardant, for example, 21 parts, 30
Part, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 99 parts.
The molecular weight of saturated polyester resin is too high, and dissolving is 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 too poor with TPU compatibility, resin after coating
The cohesive strength of composition layer is relatively low, causes peel strength inadequate.It is preferred that the number-average molecular weight Mn of the saturated polyester resin
Be 8000~30000, glass transition temperature Tg be -30 DEG C~110 DEG C between, 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, 65 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 109 DEG C；Hydroxyl value between 2~10mgKOH/g, for example
3mgKOH/g、5mgKOH/g、10mgKOH/g；Described saturated polyester resin can preferably SK Chemical of South Korea manufacture ES450,
ES850, ES750, ES901, ES600, ES120 etc., also Evonik companies of Germany manufacture S1611, S1426, S1313,
L952, L912 etc..
It is preferred that the TPU is selected from any one in PAUR or EU
Or two kinds of mixture；The fusing point of the TPU be 110 DEG C~130 DEG C, such as 115 DEG C, 120 DEG C, 125,
129℃。
It is preferred that the compatilizer is the mixed of any one or two kinds in response type compatilizer or non-reactive compatilizer
Compound.
It is preferred that the response type compatilizer is that low-molecular-weight terminal carboxyl polyester resin, isocyanate terminated based polyurethanes are pre-
The mixture of any one or two kinds in aggressiveness；The non-reactive compatilizer is the block copolymerization of saturated polyester and polyurethane
Thing.
It is preferred that the fire retardant is including any one in halogenated flame retardant, halogen system fire retarding synergist, metal hydroxides
Kind or at least two mixture；The halogenated flame retardant is TDE, brominated styrene, brominated epoxy resin, four
In the double tetrabromo phthalimides of bromine bisphenol-A, HBCD, ethylene any one or at least two mixture；
The halogen system fire retarding synergist is any one in antimony oxide, antimony pentoxide or at least two mixture；It is described
Metal hydroxides is any one in magnesium hydroxide, aluminium hydroxide or two kinds of mixture.
It is preferred that the thermoplastic resin composition also includes antioxidant, according to mass fraction meter, the antioxidant adds
Dosage is 0.1~1 part, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part.Lamination can be extended
Busbar insulated rubber film service life, slows down or suppresses the carrying out of adhesive ageing process during hot pressing, is preferably used in the present invention
Hinered phenols antioxidant 1010,1076,1098,2246 and phosphite ester kind antioxidant 168,618.
The present invention also provides a kind of adhesive, including thermoplastic resin composition as described above and organic solvent, described
The solid content of adhesive is 30wt%~60wt%, can obtain suitable viscosity, there is provided good processability, it is ensured that used (such as
Coating) during occur without visual defects.
It is preferred that the organic solvent is ethanol, propyl alcohol, isopropanol, butanol, n-amyl alcohol, cyclohexanol, isoamyl alcohol, second two
Alcohol, 1,2- propane diols, 1,3- propane diols, butanone, acetone, cyclohexanone, toluene, dimethylbenzene, glycol monoethyl ether, propane diols list first
Any one in ether, propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, dimethylacetylamide or at least two
The mixture planted.
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 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：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 described above, it is characterised in that bag
Include step：
(1) according to the mass fraction weigh TPU, saturated polyester resin, compatilizer, antioxidant and
Fire retardant, high shear dispersed with stirring equipment is used cooperatively using ball mill, jar mill or sand mill by itself and organic solvent simultaneously
Mixing, is obtained adhesive；And
(2) the adhesive single or double is coated on insulating substrate, online drying oven is sent into, 80~170
DEG C heating forms the gluing oxidant layer of solid-state in 2~10 minutes to remove the organic solvent, and winding obtains the stack bus bar and uses
Insulated rubber film.
It is preferred that the organic solvent is ethanol, propyl alcohol, isopropanol, butanol, n-amyl alcohol, cyclohexanol, isoamyl alcohol, second two
Alcohol, 1,2- propane diols, 1,3- propane diols, butanone, acetone, cyclohexanone, toluene, dimethylbenzene, glycol monoethyl ether, propane diols list first
Any one in ether, propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, dimethylacetylamide or at least two
The mixture planted.
Prior art is compared, and the present invention has the advantages that：
Thermoplastic resin composition of the invention coordinates saturated polyester tree using TPU as matrix resin
Fat, compatilizer, antioxidant and fire retardant composition.Wherein TPU has excellent pliability and resistant of high or low temperature
Can, but the shortcomings of there is loss of properties on aging, and there are problems that with the adhesive property of insulation film not；Saturated polyester tree
Fat fusing point is low, and resistance to elevated temperatures is poor, but ageing properties are good and metal and insulation film have excellent adhesive property.By heat
Plastic polyurethane resin and saturated polyester resin blending and modifying, add a small amount of compatilizer, can obtain the thermoplasticity of excellent compatibility
Resin combination, with good high temperature performance, ageing properties and adhesive property.And the resin combination is free of curing agent,
Temperature flowing is good, can meet low temperature pressing and require.Stack bus bar insulated rubber film is prepared using the thermoplastic resin composition,
With excellent high/low temperature adhesive property, high/low-temperature impact performance, low temperature pressing performance and processing characteristics.
Brief description of the drawings
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 thermoplastic resin composition, including 55 parts of PAUR, the saturated polyester calculated according to mass fraction
It is 20 parts of resin (L952), 1 part of response type compatilizer, 30 parts of antimony oxide, 55 parts of TDE, 8 parts of aluminium hydroxide, anti-
0.3 part of oxygen agent.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted by described with acetone
PAUR, saturated polyester resin, response type compatilizer, antimony oxide, TDE, aluminium hydroxide, antioxygen
The liquid dispersion (solids content 35%) of agent composition, is blended into adhesive.
As shown in figure 1, the adhesive coating machine one side is coated on the PET insulation films 10 that thickness is 125 μm again, apply
Glue thickness is 15 μm；
Then processed 8 minutes at 90 DEG C, so that acetone volatilizees, the gluing oxidant layer 20 of solid-state is formed on PET dielectric films；
Finally winding obtains the stack bus bar insulated rubber film 1 of the thermoplastic resin composition.
Embodiment 2
A kind of thermoplastic resin composition, including 63 parts of EU, the saturated polyester calculated according to mass fraction
The double tetrabromo phthalimides 40 of 13 parts of resin (S1611), 2.4 parts of non-reactive compatilizer, 21 parts of antimony pentoxide, ethylene
Part, 9 parts of magnesium hydroxide, 0.6 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted by described with butanone
The double tetrabromo phthalimides of EU, saturated polyester resin, non-reactive compatilizer, antimony pentoxide, ethylene,
The liquid dispersion (solids content 48%) of magnesium hydroxide, antioxidant composition, is blended into adhesive.
As shown in Fig. 2 be coated in the adhesive coating machine is two-sided on the PBT insulation films 10 ' that thickness is 175 μm again,
Rubberization thickness is 25 μm；
Then processed 5 minutes at 110 DEG C, so that butanone 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 thermoplastic resin composition.
Embodiment 3
A kind of thermoplastic resin composition, including 70 parts of the EU calculated according to the mass fraction, saturated polyester tree
It is 8 parts of fat (ES120), 7 parts of non-reactive compatilizer, 18 parts of antimony oxide, 38 parts of tetrabromobisphenol A, 12 parts of magnesium hydroxide, anti-
0.8 part of oxygen agent.
By the thermoplastic resin composition for stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted with dimethylformamide
Section is by the EU, saturated polyester resin, non-reactive compatilizer, antimony oxide, tetrabromobisphenol A, hydroxide
The liquid dispersion (solids content is 48%) of magnesium, antioxidant composition, is blended into adhesive.
The adhesive coating machine one side is coated on the PEN insulation films that thickness is 100 μm again, rubberization thickness is 40 μ
m；
Then processed 5 minutes at 160 DEG C, so that dimethylformamide 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 4
A kind of thermoplastic resin composition, including 50 parts of PAUR, the saturated polyester calculated according to mass fraction
It is 6 parts of resin (ES450), 1.8 parts of response type compatilizer, 7 parts of antimony oxide, 15 parts of brominated styrene, 5 parts of aluminium hydroxide, anti-
0.9 part of oxygen agent.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted with ethanol and toluene
By the PAUR, saturated polyester resin, response type compatilizer, antimony oxide, brominated styrene, aluminium hydroxide,
The liquid dispersion (solids content 60%) of antioxidant composition, is blended into adhesive.
The adhesive coating machine one side is coated on the PI insulation films that thickness is 110 μm again, rubberization thickness is 12 μm；
Then processed 9 minutes at 110 DEG C, so that ethanol and toluene volatilization, form the gluing of solid-state on PI dielectric films
Oxidant layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 5
A kind of thermoplastic resin composition, including 78 parts of PAUR, the saturated polyester calculated according to mass fraction
19 parts of resin (ES850), 5.9 parts of non-reactive compatilizer, 14 parts of antimony pentoxide, 30 parts of brominated epoxy resin, magnesium hydroxide
10 parts, 0.4 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First use propyl alcohol and dimethyl methyl
Acid amides is adjusted by the PAUR, saturated polyester resin, non-reactive compatilizer, antimony pentoxide, brominated oxygen tree
Fat, magnesium hydroxide, the liquid dispersion (solids content 45%) of antioxidant composition, are blended into adhesive.
The adhesive coating machine one side is coated on the NOMEX insulation films that thickness is 130 μm again, rubberization thickness is 17
μm；
Then processed 7 minutes at 165 DEG C, so that propyl alcohol and dimethylformamide volatilization, form 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.
Embodiment 6
A kind of thermoplastic resin composition, including 53 parts of EU, the saturated polyester calculated according to mass fraction
10 parts of resin (ES750), 3.4 parts of response type compatilizer, 12 parts of antimony oxide, 42 parts of HBCD, aluminium hydroxide 12
Part, 1.0 parts of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First use butanol and dimethyl second
Acid amides regulation by the EU, saturated polyester resin, response type compatilizer, antimony oxide, HBCD,
The liquid dispersion (solids content 57%) of aluminium hydroxide, antioxidant composition, is blended into adhesive.
The adhesive coating machine one side is coated on the PET insulation films that thickness is 150 μm again, rubberization thickness is 20 μ
m；
Then processed 6 minutes at 170 DEG C, so that butanol and dimethylacetylamide volatilization, form solid on PET dielectric films
The gluing oxidant layer of state；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 7
A kind of thermoplastic resin composition, including 74 parts of EU, the saturated polyester calculated according to mass fraction
12 parts of resin (ES901), 6.2 parts of non-reactive compatilizer, 9 parts of antimony oxide, 10 parts of antimony pentoxide, TDE
35 parts, 8 parts of aluminium hydroxide, 3 parts of magnesium hydroxide, 0.5 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted with n-amyl alcohol and butanone
Section is by the EU, saturated polyester resin, non-reactive compatilizer, antimony oxide, antimony pentoxide, ten bromines two
Vinylbenzene, aluminium hydroxide, magnesium hydroxide, the liquid dispersion (solids content 53%) of antioxidant composition, are blended into adhesive.
The adhesive coating machine one side is coated on the PBT insulation films that thickness is 140 μm again, rubberization thickness is 31 μ
m；
Then processed 7 minutes at 140 DEG C, so that n-amyl alcohol and butanone volatilization, form the glue of solid-state on PBT dielectric films
Adhesive layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 8
A kind of thermoplastic resin composition, including 59 parts of EU, the saturated polyester calculated according to mass fraction
15 parts of resin (ES600), 4.9 parts of response type compatilizer, 11 parts of antimony oxide, 12 parts of antimony pentoxide, brominated styrene 50
Part, 13 parts of aluminium hydroxide, 0.7 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted by described with toluene
EU, saturated polyester resin, response type compatilizer, antimony oxide, antimony pentoxide, brominated styrene, hydrogen-oxygen
Change aluminium, the liquid dispersion (solids content 41%) of antioxidant composition, be blended into adhesive.
The adhesive coating machine one side is coated on the PEN insulation films that thickness is 160 μm again, rubberization thickness is 38 μ
m；
Then processed 6 minutes at 130 DEG C, so that toluene volatilizees, the gluing oxidant layer of solid-state is formed on PEN dielectric films；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Embodiment 9
A kind of thermoplastic resin composition, including 82 parts of EU, the saturated polyester calculated according to mass fraction
18 parts of resin (S1426), 7.1 parts of non-reactive compatilizer, 31 parts of antimony oxide, 57 parts of brominated epoxy resin, aluminium hydroxide 8
Part, 1 part of magnesium hydroxide, 0.2 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted by institute with dimethylbenzene
State EU, saturated polyester resin, non-reactive compatilizer, antimony oxide, brominated epoxy resin, aluminium hydroxide,
The liquid dispersion (solids content 37%) of magnesium hydroxide, antioxidant composition, is blended into adhesive.
The adhesive coating machine one side is coated on the PI insulation films that thickness is 175 μm again, rubberization thickness is 42 μm；
Then processed 4 minutes at 145 DEG C, so that dimethylbenzene 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 10
A kind of thermoplastic resin composition, including 67 parts of EU, the saturated polyester calculated according to mass fraction
16 parts of resin (S1313), 5.3 parts of response type compatilizer, 28 parts of antimony oxide, 24 parts of brominated styrene, brominated epoxy resin
26 parts, 11 parts of aluminium hydroxide, 0.6 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First with ethyl acetate adjust by
The EU, saturated polyester resin, response type compatilizer, antimony oxide, brominated styrene, brominated oxygen tree
Fat, aluminium hydroxide, the liquid dispersion (solids content 32%) of antioxidant composition, are blended into adhesive.
The adhesive coating machine one side is coated on the NOMEX insulation films that thickness is 195 μm again, rubberization thickness is 47
μm；
Then processed 3 minutes at 150 DEG C, so that ethyl acetate volatilizees, the gluing of solid-state is formed on NOMEX dielectric films
Oxidant layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Comparative example 1
A kind of thermoplastic resin composition, including 70 parts of thermoplastic polyester type polyurethane, three calculated according to mass fraction
Aoxidize 15 parts of two antimony, 38 parts of brominated styrene, 5 parts of aluminium hydroxide, 0.3 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted with dimethylacetylamide
Save the liquid point being made up of the thermoplastic polyester type polyurethane, antimony oxide, brominated styrene, aluminium hydroxide, antioxidant
A prose style free from parallelism (solids content 55%), is blended into adhesive.
The adhesive coating machine one side is coated on the PET insulation films that thickness is 125 μm again, rubberization thickness is 30 μ
m；
Then processed 3 minutes at 170 DEG C, so that dimethylacetylamide volatilizees, the glue of solid-state is formed on PET dielectric films
Adhesive layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
Comparative example 2
A kind of thermoplastic resin composition, including 20 parts of saturated polyester resin (ES901), five calculated according to mass fraction
Aoxidize 5 parts of two antimony, 18 parts of TDE, 0.8 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted by described with acetone
Saturated polyester resin, antimony pentoxide, TDE, the liquid dispersion (solids content 48%) of antioxidant composition, mix
It is made adhesive.
The adhesive coating machine one side is coated on the PET insulation films that thickness is 188 μm again, rubberization thickness is 40 μ
m；
Then processed 1 minute at 100 DEG C, so that acetone 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.
Comparative example 3
A kind of thermoplastic resin composition, including 70 parts of the thermoplastic polyether urethane, full calculated according to mass fraction
With 10 parts of polyester resin (ES600), 18 parts of antimony oxide, 42 parts of tetrabromobisphenol A, 0.2 part of antioxidant.
Described thermoplastic resin composition is applied to stack bus bar insulated rubber film.
The preparation method of the stack bus bar insulated rubber film containing thermoplastic resin composition：First adjusted with dimethylacetylamide
The liquid that section is made up of the thermoplastic polyether urethane, saturated polyester resin, antimony oxide, tetrabromobisphenol A, antioxidant
Dispersion (solids content 40%), is blended into adhesive.
The adhesive coating machine one side is coated on the PBT insulation films that thickness is 120 μm again, rubberization thickness is 35 μ
m；
Then processed 5 minutes at 170 DEG C, so that dimethylacetylamide volatilizees, the glue of solid-state is formed on PBT dielectric films
Adhesive layer；
Finally winding obtains the stack bus bar insulated rubber film of the thermoplastic resin composition.
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) low temperature pressing property
Insulated rubber film and tin-coated copper bar are without foaming, delamination, cracking, then otherwise unqualified for qualified in 130 DEG C of pressings.
(2) 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.
(3) electrical strength
After insulated rubber film connection equipment, making alive, frequency is 50Hz, electrical strength when calculating punctures.
(4) elongation percentage
By ASTM D-882 standards, obtained using material stretch test machine test.
(5) 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.
(6) high/low-temperature impact performance
By insulated rubber film and tin-coated copper bar high-temperature laminating, high and low temperature impact test is then carried out.High and low temperature impact test bar
Part is：- 40 DEG C~105 DEG C/200 times circulations, -40 DEG C/constant temperature 0.5 hour, -40 DEG C are warming up to 105 DEG C/1 minute, 105 DEG C/permanent
Temperature 0.5 hour, 105 DEG C are 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 tin-coated copper bar without foaming, without cracking after high/low-temperature impact.
(7) hydrothermal aging performance
By insulated rubber film and tin-coated copper bar high-temperature laminating, hydrothermal aging experiment is then carried out.Hydrothermal aging experimental condition is：
85 DEG C × 85%RH/1000 hours.
After hydrothermal aging between glued membrane and tin-coated copper bar without foaming, delamination, cracking then for qualified, it is otherwise unqualified.
(8) processability (bending test)
By thickness to be cooled to room temperature after the tin-coated copper bar and glued membrane high-temperature laminating of 3mm, folding test, bending angle are carried out
It is 90 °.It is otherwise unqualified without foaming, delamination, cracking then for qualified between glued membrane and tin-coated copper bar after bending.
(9) high temperature test
The sample of Bending Processing is placed in into 105 DEG C of baking ovens to toast 240 hours, between glued membrane and tin-coated copper bar without foaming, delamination,
It is then qualified to ftracture, otherwise unqualified.
(10) anti-flammability
Determined according to the vertical combustions of UL 94.
Specific test result is as shown in table 1 below.
As known from Table 1, TPU is used alone in comparative example 1, its adhesive property with PET film compared with
Difference, A state peel strengths are only 0.42N/mm, but TPU fusing point is higher than 105 DEG C, therefore 105 DEG C of high temperature are peeled off
Intensity is up to 0.85N/mm；In comparative example 2, individually using saturated polyester resin, A states peel strength is higher than comparative example 1, but its
Resistance to elevated temperatures is poor, and 105 DEG C of high temperature peel strengths are only 0.08N/mm；In comparative example 3, by saturated polyester and thermoplastic poly ammonia
Ester is blended, and is not added with compatilizer, causes both compatibilities poor, therefore A state peel strengths are only 0.37N/mm, and 105 DEG C are peeled off by force
Degree is only 0.11N/mm.High/low-temperature impact performance, resistance to elevated temperatures, the hydrothermal aging performance of the insulated rubber film prepared in comparative example
And processing characteristics is unqualified.And after TPU is blended with saturated polyester resin in embodiment, add appropriate phase
Hold agent, the good thermoplastic resin composition of compatibility can be obtained, low temperature pressure can be met in being pressed at 130 DEG C with tin-coated copper bar
Close and require, its A states peel strength is more than 2.0N/mm, and 105 DEG C of peel strengths are more than 1.0N/mm, with good high/low-temperature impact
Performance, resistance to elevated temperatures, hydrothermal aging performance and processing characteristics, properties are superior to comparative example and existing product.
In sum, the electrical resistance of the stack bus bar insulated rubber film of thermoplastic resin composition of the invention and its preparation
Energy, resistance to environmental testing are up to standard, and anti-flammability reaches UL94VTM-0 grades, than more than 20 DEG C of existing product pressing-in temp reduction, and tool
There are excellent high/low temperature peel strength, good processing characteristics, the performance requirement that low temperature presses stack bus bar 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 (13)
1. a kind of thermoplastic resin composition, it is characterised in that according to mass fraction meter, the thermoplastic resin composition includes
Following component：
2. thermoplastic resin composition as claimed in claim 1, it is characterised in that the equal molecule of number of the saturated polyester resin
It is 8000~30000 to measure, and glass transition temperature is between -30 DEG C~110 DEG C, hydroxyl value is between 2~10mgKOH/g；It is described
Saturated polyester resin be selected from ES450, ES850, ES750, ES901, ES600, ES120, S1611, S1426, S1313, L952 or
In L912 any one or at least two mixture.
3. thermoplastic resin composition as claimed in claim 1, it is characterised in that the TPU is selected from poly-
The mixture of any one or two kinds in ester type polyurethane or EU；The fusing point of the TPU
It is 110 DEG C~130 DEG C.
4. thermoplastic resin composition as claimed in claim 1, it is characterised in that the compatilizer be response type compatilizer or
The mixture of any one or two kinds in non-reactive compatilizer.
5. thermoplastic resin composition as claimed in claim 4, it is characterised in that the response type compatilizer is low-molecular-weight
The mixture of any one or two kinds in terminal carboxyl polyester resin, terminal isocyanate group base polyurethane prepolymer for use as；The non-reaction
Type compatilizer is the block copolymer of saturated polyester and polyurethane.
6. thermoplastic resin composition as claimed in claim 1, it is characterised in that the fire retardant include halogenated flame retardant,
In halogen system fire retarding synergist, metal hydroxides 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 hydroxides is any one in magnesium hydroxide, aluminium hydroxide
Or two kinds of mixture.
7. thermoplastic resin composition as claimed in claim 1, it is characterised in that also including antioxidant, according to mass fraction
Meter, the addition of the antioxidant is 0.1~1 part, the antioxidant be selected from Hinered phenols antioxidant 1010,1076,1098,
2246 and phosphite ester kind antioxidant 168,618 in any one or at least two mixture.
8. a kind of adhesive, it is characterised in that including the thermoplastic resin composition as described in any one of claim 1~7 and
Organic solvent, the solid content of the adhesive is 30wt%~60wt%.
9. adhesive as claimed in claim 8, it is characterised in that the organic solvent be ethanol, propyl alcohol, isopropanol, butanol,
N-amyl alcohol, cyclohexanol, isoamyl alcohol, ethylene glycol, 1,2- propane diols, 1,3- propane diols, butanone, acetone, cyclohexanone, toluene, diformazan
Benzene, glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, dimethyl
In acetamide any one or at least two mixture.
10. a kind of stack bus bar insulated rubber film, it is characterised in that including insulation film and single or double be coated on it is described absolutely
The gluing oxidant layer that the adhesive as described in any one of claim 8~9 on edge film is formed.
11. stack bus bar insulated rubber films as claimed in claim 10, 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.
12. stack bus bar insulated rubber films as claimed in claim 10, 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 13. methods of the stack bus bar insulated rubber film prepared as described in any one of claim 10~12, its feature exists
In, including step：
(1) TPU, saturated polyester resin, compatilizer and fire retardant are weighed according to the mass fraction, and is had
Machine solvent is mixed to prepare adhesive；And
(2) the adhesive single or double is coated on insulating substrate, feeding baking oven is formed with removing the organic solvent
The gluing oxidant layer of solid-state, winding obtains the stack bus bar insulated rubber film.
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| CN108864924A (en) * | 2018-07-04 | 2018-11-23 | 湖北恒驰电子科技有限公司 | A kind of halogen-free resin composition and the flexible printed-circuit board cover film prepared with it |
| CN109280503A (en) * | 2018-08-21 | 2019-01-29 | 项正 | A kind of Packaging Aluminum Foil composite material and preparation method |
| CN112757710A (en) * | 2021-01-09 | 2021-05-07 | 杭州晶硝子玻璃科技有限公司 | Anti-deformation low-reflection glass and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108753167A (en) * | 2018-05-15 | 2018-11-06 | 广东生益科技股份有限公司 | A kind of resin combination, the stack bus bar insulated rubber film and preparation method thereof comprising it |
| CN108753167B (en) * | 2018-05-15 | 2020-08-18 | 广东生益科技股份有限公司 | Resin composition, insulating glue film containing resin composition for laminated busbar and preparation method of insulating glue film |
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| CN109280503A (en) * | 2018-08-21 | 2019-01-29 | 项正 | A kind of Packaging Aluminum Foil composite material and preparation method |
| CN112757710A (en) * | 2021-01-09 | 2021-05-07 | 杭州晶硝子玻璃科技有限公司 | Anti-deformation low-reflection glass and preparation method thereof |
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Application publication date: 20170524 |