CN109486189A - A kind of TPI film and preparation method thereof for FPC industry - Google Patents
A kind of TPI film and preparation method thereof for FPC industry Download PDFInfo
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Abstract
The invention proposes a kind of TPI films for FPC industry, it is characterized in that, being prepared from the following materials: thermoplastic polyimide resin, inorganic filler, coupling agent, graphene, conducting particles, plasticizer, triethanolamine, three (Lauryl Alcohol) esters, three (16 carbon alcohol) esters and polyethylene glycol.The present invention is modified inorganic filler, conducting particles and graphene using coupling agent, to which the thermoplastic polyimide film for guaranteeing prepared not only has good mechanical property, there is excellent dielectric constant, agent of low hygroscopicity etc. simultaneously, the application suitable for FPC industry.
Description
Technical field
The present invention relates to macromolecule membrane technical fields, and in particular to a kind of TPI film for FPC industry.
Background technique
FPC is the abbreviation of Flexible PrintedCircuit, also known as flexible printed circuit board, is with insulation flexible
Printed circuit board made of substrate has the advantages that many rigid printed circuit plates do not have, its Distribution density height, weight
Gently, thickness is thin, bending is good.It can be substantially reduced the volume of electronic product using FPC, meet electronic product to high density, small-sized
Change, the direction of high reliability development.Therefore, FPC is in space flight, military affairs, mobile communication, laptop computer, computer peripheral equipment, intelligent hand
It is widely used on the fields such as machine, digital camera or product.FPC also have good thermal diffusivity and solderability and easily
In load, overall cost is lower the advantages that.With the growth of smart electronics product sales volume in recent years, FPC, which is used as, is suitable for intelligence
The printed circuit board of electronic product becomes one of the beneficiary of smart electronics industry development.
In recent years, with the rapid development of electronic industry, electronic equipment gradually tends to miniaturization, slimming and Gao Gongneng
Change, requirement of the high-tech sectors such as communication, industrial automation, aerospace to package substrate in electronic equipment also increasingly
It is high.The high speed development of present electronics and IT products especially microwave device, densification, digitlization, high frequency and in Special Ring
In border using etc. requirements propose huge challenge to general high frequency plate and its manufacturing process.For being answered in high frequency field
Thermoplastic polyimide (TPI) material need to have excellent dielectric properties i.e. low-k and low-dielectric loss because
Son.
Thermoplastic polyimide (TPI) is compared with thermosetting property, in addition to glass transition temperature with higher, high temperature resistant and excellent
Electrical property other than, also there is good hot-working character, be mainly reflected in hot pressing, hot extrusion and injection molding, thus can
The complexity for greatly reducing equipment improves the competitiveness of domestic film.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of for the TPI film of FPC industry and its preparation side
Method, it is intended that a kind of TPI film is provided, by changing using coupling agent to inorganic filler, conducting particles and graphene
Property, so that it passes through chemical bonds, the interface binding power of raising filler and resin, thus prepared by guarantee with molecular resin
Thermoplastic polyimide film not only has good mechanical property, while there is excellent dielectric constant, agent of low hygroscopicity etc., it fits
Application for FPC industry.
The present invention provides a kind of TPI film for FPC industry, is prepared from the following materials: thermoplastic polyimide
Resin, inorganic filler, coupling agent, graphene, conducting particles, plasticizer, triethanolamine, three (Lauryl Alcohol) esters, three (16 carbon
Alcohol) ester and polyethylene glycol；
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is selected from
Pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and bisphenol-A two
One or more of acid anhydride；The diamines is selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 4,4 '-diamino
Diphenyl sulfide, 3,3 '-diamino diphenyl sulfones, ethylenediamine, 1,2- propane diamine and 1, one or more of 3- propane diamine.
As further improvement of the invention, it is prepared by weight by following raw material: thermoplastic polyimide resin
100-120 parts, 20-40 parts of inorganic filler, 1-5 parts of coupling agent, 3-10 parts of graphene, 5-12 parts of conducting particles, plasticizer 2-7
Part, 3-10 parts of triethanolamine, 1-5 parts of three (Lauryl Alcohol) ester, 2-3 parts and polyethylene glycol 50-70 parts of three (16 carbon alcohol) esters.
As further improvement of the invention, it is prepared by weight by following raw material: thermoplastic polyimide resin
105-115 parts, 25-35 parts of inorganic filler, 2-4 parts of coupling agent, 4-8 parts of graphene, 7-10 parts of conducting particles, 3-6 parts of plasticizer,
4-8 parts of triethanolamine, 2-4 parts of three (Lauryl Alcohol) ester, 2.2-2.7 parts and polyethylene glycol 55-65 parts of three (16 carbon alcohol) ester.
As further improvement of the invention, it is prepared by weight by following raw material: thermoplastic polyimide resin
110 parts, 30 parts of inorganic filler, 3 parts of coupling agent, 6 parts of graphene, 8 parts of conducting particles, 5 parts of plasticizer, 6 parts of triethanolamine, three
3 parts of (Lauryl Alcohol) ester, 2.5 parts and 60 parts of polyethylene glycol of three (16 carbon alcohol) ester.
As further improvement of the invention, the conducting particles is prepared by following methods: the nitric acid for being 3:1 by molar ratio
Silver and copper nitrate are dissolved in the nitric acid solution of 2mol/L, and mixed solution is obtained by filtration, and adjust reaction system with the ammonium hydroxide of 2mol/L
PH value silver nitrate and copper nitrate are added dropwise with 1 drop/s speed in the reactor of Xiang Shengyou distilled water when being warming up to 60 DEG C
Mix acid liquor, while the rate of addition by adjusting lye is 2 come the pH value of control system, after being added dropwise, the reaction was continued
2h, obtains yellow mercury oxide, still aging 10h, and filtering is washed with distilled water precipitating, then washed with dehydrated alcohol, is co-precipitated
Hydroxide precursor, gained presoma is dried at 105 DEG C, is ground, is warming up to 700 in Muffle furnace with 5 DEG C/min
DEG C, 2h is kept the temperature, conducting particles is obtained.
As further improvement of the invention, the coupling agent is selected from silane coupling agent or metatitanic acid containing chain alkyl
Esters coupling agent.
As further improvement of the invention, the carbon chain lengths of the chain alkyl are 8~25 carbon atoms.
As further improvement of the invention, the inorganic filler is selected from aluminium nitride, silicon nitride, magnesium nitride, beryllium nitride, nitrogen
Change one or more of boron, aluminium oxide, silica, magnesia, calcium oxide, beryllium oxide and boron oxide.
As further improvement of the invention, the plasticizer is selected from phthalic acid two (2- ethyl hexyl) ester, adjacent benzene two
Formic acid dioctyl ester, di-n-octyl phthalate, BBP(Butyl Benzyl Phthalate, di-sec-octyl phthalate, phthalic acid
Dicyclohexyl maleate, dibutyl phthalate, repefral, diethyl phthalate, the different nonyl of phthalic acid two
One or more of ester, diisooctyl phthalate and diisobutyl phthalate
The present invention further protects a kind of preparation method of above-mentioned TPI film for FPC industry, makes in accordance with the following methods
It is standby: inorganic filler, graphene, conducting particles and coupling agent are dissolved in polyethylene glycol, stir 1-5h at a temperature of 30 DEG C -70 DEG C,
Obtain the modified dispersion liquid of surface coupling agent；The modified dispersion liquid of surface coupling agent and thermoplastic polyimide resin are mixed, stirred
Plasticizer, triethanolamine, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters are added after mixing uniformly, is heated to 70 DEG C -90 DEG C and stirs
After mixing reaction 5-7h, modified thermoplastic polyimide resin, deaeration, by the polyamic acid resin after deaeration through piping are obtained
In indentation curtain coating mouth, it is cast on steel band by self weight, under the conditions of 100 DEG C -200 DEG C, solidification is dried using hot wind, is obtained
TPI film.
The invention has the following beneficial effects: the present invention using coupling agent to inorganic filler, conducting particles and graphene into
Row is modified, so that it passes through chemical bonds, the interface binding power of raising filler and resin, to guarantee made with molecular resin
Standby thermoplastic polyimide film not only has good mechanical property, while having excellent dielectric constant, agent of low hygroscopicity
Deng application suitable for FPC industry.
Detailed description of the invention
Fig. 1 is the preparation technology figure of TPI film.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general
Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work
Range.
The preparation of 1 TPI film of embodiment
Raw material forms (parts by weight): 100 parts of thermoplastic polyimide resin, 10 parts of aluminium oxide, contains 25 at 10 parts of boron nitride
5 parts of 3 parts of 1 part of silane coupling agent, graphene, conducting particles, (the 2- ethyl of phthalic acid two of the chain alkyl of a carbon atom
Oneself) 2 parts of ester, 3 parts of triethanolamine, three 1 part of (Lauryl Alcohol) esters, 2 parts and 50 parts of polyethylene glycol of three (16 carbon alcohol) esters.
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is equal
Pyromellitic dianhydride, the diamines are 4,4 '-diaminodiphenyl ethers.
Conducting particles is prepared by following methods: silver nitrate and copper nitrate that molar ratio is 3:1 are dissolved in the nitric acid of 2mol/L
In solution, mixed solution is obtained by filtration, the pH value of reaction system, when being warming up to 60 DEG C, Xiang Sheng are adjusted with the ammonium hydroxide of 2mol/L
There is the mix acid liquor that silver nitrate and copper nitrate is added dropwise in the reactor of distilled water with 1 drop/s speed, while by adjusting lye
Rate of addition to carry out the pH value of control system be 2, after being added dropwise, the reaction was continued 2h, obtain yellow mercury oxide, it is still aging
10h, filtering, is washed with distilled water precipitating, then washed with dehydrated alcohol, the hydroxide precursor being co-precipitated, by gained
Presoma is dried at 105 DEG C, is ground, and is warming up to 700 DEG C in Muffle furnace with 5 DEG C/min, is kept the temperature 2h, is obtained conducting particles.
TPI film is prepared by following methods: by boron nitride, aluminium oxide, graphene, conducting particles and containing 25 carbon atoms
The silane coupling agent of chain alkyl be dissolved in polyethylene glycol, stir 1-5h at a temperature of 30 DEG C, it is modified to obtain surface coupling agent
Dispersion liquid；The modified dispersion liquid of surface coupling agent and thermoplastic polyimide resin are mixed, O-phthalic is stirring evenly and then adding into
Sour two (2- ethyl hexyl) esters, triethanolamine, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters, are heated to 70 and are stirred to react 5h
Afterwards, modified thermoplastic polyimide resin is obtained, the polyamic acid resin after deaeration is pressed into curtain coating mouth through piping by deaeration
In, it is cast on steel band by self weight, under the conditions of 100 DEG C, solidification is dried using hot wind, obtains TPI film.
The preparation of 2 TPI film of embodiment
Raw material forms (parts by weight): 120 parts of thermoplastic polyimide resin, 40 parts of silicon nitride, containing 15 carbon atoms
7 parts of 12 parts of 10 parts of 5 parts of silane coupling agent, graphene, conducting particles, repefral, the triethanolamine of chain alkyl
10 parts, three 5 parts of (Lauryl Alcohol) esters, 3 parts and 70 parts of polyethylene glycol of three (16 carbon alcohol) esters.
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is 3,
3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, the diamines are 3,4 '-diaminodiphenyl ethers.
Conducting particles is prepared by following methods: silver nitrate and copper nitrate that molar ratio is 3:1 are dissolved in the nitric acid of 2mol/L
In solution, mixed solution is obtained by filtration, the pH value of reaction system, when being warming up to 60 DEG C, Xiang Sheng are adjusted with the ammonium hydroxide of 2mol/L
There is the mix acid liquor that silver nitrate and copper nitrate is added dropwise in the reactor of distilled water with 1 drop/s speed, while by adjusting lye
Rate of addition to carry out the pH value of control system be 2, after being added dropwise, the reaction was continued 2h, obtain yellow mercury oxide, it is still aging
10h, filtering, is washed with distilled water precipitating, then washed with dehydrated alcohol, the hydroxide precursor being co-precipitated, by gained
Presoma is dried at 105 DEG C, is ground, and is warming up to 700 DEG C in Muffle furnace with 5 DEG C/min, is kept the temperature 2h, is obtained conducting particles.
TPI film is prepared by following methods: by silicon nitride, graphene, conducting particles and long-chain containing 15 carbon atoms
The silane coupling agent of alkyl is dissolved in polyethylene glycol, stirs 5h at a temperature of 70 DEG C, obtains the modified dispersion liquid of surface coupling agent；It will
The modified dispersion liquid of surface coupling agent and thermoplastic polyimide resin mixing, be stirring evenly and then adding into repefral,
Triethanolamine, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters, be heated to 90 DEG C be stirred to react 7h after, obtain modified thermoplastic
Property polyimide resin, deaeration, by the polyamic acid resin after deaeration through piping be pressed into curtain coating mouth in, be cast to steel by self weight
It takes, under the conditions of 200 DEG C, solidification is dried using hot wind, obtains TPI film.
The preparation of 3 TPI film of embodiment
Raw material forms (parts by weight): 105 parts of thermoplastic polyimide resin, contains 10 carbon atoms at 25 parts of silica
Chain alkyl 3 parts of 7 parts of 4 parts of 2 parts of silane coupling agent, graphene, conducting particles, diisononyl phthalate, three ethyl alcohol
4 parts of amine, three 2 parts of (Lauryl Alcohol) esters, 2.2 parts and 55 parts of polyethylene glycol of three (16 carbon alcohol) esters.
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is 3,
3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, the diamines are 3,3 '-diamino diphenyl sulfones.
Conducting particles is prepared by following methods: silver nitrate and copper nitrate that molar ratio is 3:1 are dissolved in the nitric acid of 2mol/L
In solution, mixed solution is obtained by filtration, the pH value of reaction system, when being warming up to 60 DEG C, Xiang Sheng are adjusted with the ammonium hydroxide of 2mol/L
There is the mix acid liquor that silver nitrate and copper nitrate is added dropwise in the reactor of distilled water with 1 drop/s speed, while by adjusting lye
Rate of addition to carry out the pH value of control system be 2, after being added dropwise, the reaction was continued 2h, obtain yellow mercury oxide, it is still aging
10h, filtering, is washed with distilled water precipitating, then washed with dehydrated alcohol, the hydroxide precursor being co-precipitated, by gained
Presoma is dried at 105 DEG C, is ground, and is warming up to 700 DEG C in Muffle furnace with 5 DEG C/min, is kept the temperature 2h, is obtained conducting particles.
TPI film is prepared by following methods: by silica, graphene, conducting particles and length containing 10 carbon atoms
The silane coupling agent of alkyl group is dissolved in polyethylene glycol, stirs 2h at a temperature of 40 DEG C, obtains the modified dispersion liquid of surface coupling agent；
The modified dispersion liquid of surface coupling agent and thermoplastic polyimide resin are mixed, the different nonyl of phthalic acid two is stirring evenly and then adding into
Ester, triethanolamine, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters, be heated to 80 DEG C be stirred to react 6h after, obtain modified
Polyamic acid resin after deaeration is pressed into curtain coating mouth through piping, is cast by self weight by thermoplastic polyimide resin, deaeration
To steel band, under the conditions of 120 DEG C, solidification is dried using hot wind, obtains TPI film.
The preparation of 4 TPI film of embodiment
Raw material forms (parts by weight): 115 parts of thermoplastic polyimide resin, 20 parts of boron oxide, contains 8 at 15 parts of beryllium oxide
10 parts of 8 parts of 4 parts of silane coupling agent, graphene, conducting particles, the diisobutyl phthalate 6 of the chain alkyl of a carbon atom
Part, 8 parts of triethanolamine, three 4 parts of (Lauryl Alcohol) esters, 2.7 parts and 65 parts of polyethylene glycol of three (16 carbon alcohol) esters.
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is double
Phenol A dianhydride, the diamines are 4,4 '-diaminodiphenyl sulfides.
Conducting particles is prepared by following methods: silver nitrate and copper nitrate that molar ratio is 3:1 are dissolved in the nitric acid of 2mol/L
In solution, mixed solution is obtained by filtration, the pH value of reaction system, when being warming up to 60 DEG C, Xiang Sheng are adjusted with the ammonium hydroxide of 2mol/L
There is the mix acid liquor that silver nitrate and copper nitrate is added dropwise in the reactor of distilled water with 1 drop/s speed, while by adjusting lye
Rate of addition to carry out the pH value of control system be 2, after being added dropwise, the reaction was continued 2h, obtain yellow mercury oxide, it is still aging
10h, filtering, is washed with distilled water precipitating, then washed with dehydrated alcohol, the hydroxide precursor being co-precipitated, by gained
Presoma is dried at 105 DEG C, is ground, and is warming up to 700 DEG C in Muffle furnace with 5 DEG C/min, is kept the temperature 2h, is obtained conducting particles.
TPI film is prepared by following methods: by beryllium oxide, boron oxide, graphene, conducting particles and containing 8 carbon atoms
The silane coupling agent of chain alkyl be dissolved in polyethylene glycol, stir 4h at a temperature of 60 DEG C, obtain modified point of surface coupling agent
Dispersion liquid；The modified dispersion liquid of surface coupling agent and thermoplastic polyimide resin are mixed, phthalic acid is stirring evenly and then adding into
Diisobutyl ester, triethanolamine, three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters, be heated to 80 DEG C be stirred to react 6h after, obtain
Polyamic acid resin after deaeration is pressed into curtain coating mouth, by certainly by modified thermoplastic polyimide resin, deaeration through piping
Density current is extended down on steel band, under the conditions of 180 DEG C, solidification is dried using hot wind, obtains TPI film.
The preparation of 5 TPI film of embodiment
Raw material forms (parts by weight): 110 parts of thermoplastic polyimide resin, 30 parts of calcium oxide, titante coupling agent 3
Part, 6 parts of graphene, 8 parts of conducting particles, 5 parts of dicyclohexyl phthalate, 6 parts of triethanolamine, three 3 parts of (Lauryl Alcohol) esters,
Three 2.5 parts of (16 carbon alcohol) esters and 60 parts of polyethylene glycol.
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is 3,
3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, the diamines are 1,2- propane diamine.
Conducting particles is prepared by following methods: silver nitrate and copper nitrate that molar ratio is 3:1 are dissolved in the nitric acid of 2mol/L
In solution, mixed solution is obtained by filtration, the pH value of reaction system, when being warming up to 60 DEG C, Xiang Sheng are adjusted with the ammonium hydroxide of 2mol/L
There is the mix acid liquor that silver nitrate and copper nitrate is added dropwise in the reactor of distilled water with 1 drop/s speed, while by adjusting lye
Rate of addition to carry out the pH value of control system be 2, after being added dropwise, the reaction was continued 2h, obtain yellow mercury oxide, it is still aging
10h, filtering, is washed with distilled water precipitating, then washed with dehydrated alcohol, the hydroxide precursor being co-precipitated, by gained
Presoma is dried at 105 DEG C, is ground, and is warming up to 700 DEG C in Muffle furnace with 5 DEG C/min, is kept the temperature 2h, is obtained conducting particles.
TPI film is prepared by following methods: calcium oxide, graphene, conducting particles and titante coupling agent being dissolved in poly-
Ethylene glycol stirs 3.5h at 50 °C, obtains the modified dispersion liquid of surface coupling agent；By the modified dispersion liquid of surface coupling agent
It is mixed with thermoplastic polyimide resin, is stirring evenly and then adding into dicyclohexyl phthalate, triethanolamine, three (12 carbon
Alcohol) ester and three (16 carbon alcohol) esters, be heated to 80 DEG C be stirred to react 6h after, obtain modified thermoplastic polyimide resin, take off
Polyamic acid resin after deaeration is pressed into curtain coating mouth through piping, is cast on steel band by self weight, in 150 DEG C of conditions by bubble
Under, solidification is dried using hot wind, obtains TPI film.
1 performance test of test case
TPI film prepared by 1-5 of the embodiment of the present invention is tested for the property, the results are shown in Table 1.
1 the performance test results table of table
As seen from the above table, the TPI film of preparation of the embodiment of the present invention has preferable comprehensive performance, can be widely used in
In FPC industry.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also
Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by
The range of claims determines.
Claims (10)
1. a kind of TPI film for FPC industry, which is characterized in that be prepared from the following materials: thermoplastic polyimide tree
Rouge, inorganic filler, coupling agent, graphene, conducting particles, plasticizer, triethanolamine, three (Lauryl Alcohol) esters, three (16 carbon
Alcohol) ester and polyethylene glycol；
The thermoplastic polyimide resin is that 0.8-1.2 is synthesized by dianhydride and diamines in molar ratio, and the dianhydride is selected from equal benzene
Tetracarboxylic acid dianhydride, 3, in 3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and bisphenol A dianhydride
One or more；The diamines is selected from 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 4,4 '-diamino hexichol
Thioether, 3,3 '-diamino diphenyl sulfones, ethylenediamine, 1,2- propane diamine and 1, one or more of 3- propane diamine.
2. a kind of TPI film for FPC industry according to claim 1, which is characterized in that by weight by following raw material
It is prepared: 100-120 parts of thermoplastic polyimide resin, 20-40 parts of inorganic filler, 1-5 parts of coupling agent, graphene 3-10
Part, 5-12 parts of conducting particles, 2-7 parts of plasticizer, 3-10 parts of triethanolamine, 1-5 parts of three (Lauryl Alcohol) ester, three (16 carbon alcohol)
2-3 parts and polyethylene glycol 50-70 parts of ester.
3. a kind of TPI film for FPC industry according to claim 2, which is characterized in that by weight by following raw material
Be prepared: 105-115 parts of thermoplastic polyimide resin, 25-35 parts of inorganic filler, 2-4 parts of coupling agent, 4-8 parts of graphene,
7-10 parts of conducting particles, 3-6 parts of plasticizer, 4-8 parts of triethanolamine, 2-4 parts of three (Lauryl Alcohol) ester, three (16 carbon alcohol) esters
2.2-2.7 part and 55-65 parts of polyethylene glycol.
4. a kind of TPI film for FPC industry according to claim 3, which is characterized in that by weight by following raw material
It is prepared: 110 parts of thermoplastic polyimide resin, 30 parts of inorganic filler, 3 parts of coupling agent, 6 parts of graphene, conducting particles 8
Part, 5 parts of plasticizer, 6 parts of triethanolamine, three 3 parts of (Lauryl Alcohol) esters, 2.5 parts and 60 parts of polyethylene glycol of three (16 carbon alcohol) esters.
5. a kind of TPI film for FPC industry according to claim 1, which is characterized in that the conducting particles is by following
Method preparation: silver nitrate and copper nitrate that molar ratio is 3:1 are dissolved in the nitric acid solution of 2mol/L, it is molten that mixing is obtained by filtration
Liquid adjusts the pH value of reaction system with the ammonium hydroxide of 2mol/L, when being warming up to 60 DEG C, with 1 in the reactor of Xiang Shengyou distilled water
The mix acid liquor of silver nitrate and copper nitrate is added dropwise in drop/s speed, while the rate of addition by adjusting lye is come control system
PH value is 2, and after being added dropwise, the reaction was continued 2h obtains yellow mercury oxide, and still aging 10h, filtering, it is heavy to be washed with distilled water
It forms sediment, then is washed with dehydrated alcohol, the hydroxide precursor being co-precipitated, gained presoma is dried at 105 DEG C, is ground
Mill is warming up to 700 DEG C in Muffle furnace with 5 DEG C/min, keeps the temperature 2h, obtains conducting particles.
6. a kind of TPI film for FPC industry according to claim 1, which is characterized in that the coupling agent, which is selected from, to be contained
The silane coupling agent or titante coupling agent of chain alkyl.
7. a kind of TPI film for FPC industry according to claim 6, which is characterized in that the carbochain of the chain alkyl
Length is 8~25 carbon atoms.
8. a kind of TPI film for FPC industry according to claim 1, which is characterized in that the inorganic filler is selected from nitrogen
Change aluminium, silicon nitride, magnesium nitride, beryllium nitride, boron nitride, aluminium oxide, silica, magnesia, calcium oxide, beryllium oxide and boron oxide
One or more of.
9. a kind of TPI film for FPC industry according to claim 1, which is characterized in that the plasticizer is selected from adjacent benzene
Dioctyl phthalate two (2- ethyl hexyl) ester, dioctyl phthalate, di-n-octyl phthalate, BBP(Butyl Benzyl Phthalate, neighbour
Phthalic acid di-sec-octyl, dicyclohexyl phthalate, dibutyl phthalate, repefral, adjacent benzene two
One of formic acid diethylester, diisononyl phthalate, diisooctyl phthalate and diisobutyl phthalate
Or it is several.
10. a kind of preparation method of the TPI film for FPC industry described in -9 any claims according to claim 1, special
Sign is, prepares in accordance with the following methods: inorganic filler, graphene, conducting particles and coupling agent being dissolved in polyethylene glycol, 30
1-5h is stirred at a temperature of DEG C -70 DEG C, obtains the modified dispersion liquid of surface coupling agent；By the modified dispersion liquid of surface coupling agent and thermoplastic
Property polyimide resin mixing, be stirring evenly and then adding into plasticizer, triethanolamine, three (Lauryl Alcohol) esters and three (16 carbon alcohol)
Ester, be heated to 70 DEG C -90 DEG C be stirred to react 5-7h after, obtain modified thermoplastic polyimide resin, deaeration, after deaeration
Polyamic acid resin is pressed into curtain coating mouth through piping, is cast on steel band by self weight, under the conditions of 100 DEG C -200 DEG C, is used
Solidification is dried in hot wind, obtains TPI film.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4433965A (en) * | 1980-02-25 | 1984-02-28 | Nippondenso Co., Ltd. | Torque transmission belt means |
| CN1502661A (en) * | 2002-09-13 | 2004-06-09 | 钟渊化学工业株式会社 | Polyimide film, mfg method and application |
| CN101027345A (en) * | 2004-09-24 | 2007-08-29 | 株式会社钟化 | Novel polyimide film and adhesive film and flexible metal-clad laminate both obtained with the same |
| CN101627074A (en) * | 2006-06-26 | 2010-01-13 | 沙伯基础创新塑料知识产权有限公司 | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
| CN102627856A (en) * | 2012-04-01 | 2012-08-08 | 云南云天化股份有限公司 | Polyimide film of high-peel-strength flexible printed circuit board, preparation method thereof and printed circuit board made of polyimide film |
| CN102712754A (en) * | 2009-11-20 | 2012-10-03 | E.I.内穆尔杜邦公司 | Coverlay compositions and methods relating thereto |
| CN102918088A (en) * | 2010-03-30 | 2013-02-06 | 可隆工业株式会社 | Polyimide film |
| CN104031277A (en) * | 2013-03-07 | 2014-09-10 | 东丽·杜邦股份有限公司 | Polyimide film and manufacturing method thereof |
| CN104053724A (en) * | 2012-01-20 | 2014-09-17 | 旭化成电子材料株式会社 | Resin Composition, Layered Product, Multilayered Printed Wiring Board, Multilayered Flexible Wiring Board, And Process For Producing Same |
| CN104774461A (en) * | 2015-04-29 | 2015-07-15 | 江苏亚宝绝缘材料股份有限公司 | Polyimide film prepared through carbonyl dianhydride and diamine |
-
2018
- 2018-11-09 CN CN201811332975.9A patent/CN109486189A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4433965A (en) * | 1980-02-25 | 1984-02-28 | Nippondenso Co., Ltd. | Torque transmission belt means |
| CN1502661A (en) * | 2002-09-13 | 2004-06-09 | 钟渊化学工业株式会社 | Polyimide film, mfg method and application |
| CN101027345A (en) * | 2004-09-24 | 2007-08-29 | 株式会社钟化 | Novel polyimide film and adhesive film and flexible metal-clad laminate both obtained with the same |
| CN101627074A (en) * | 2006-06-26 | 2010-01-13 | 沙伯基础创新塑料知识产权有限公司 | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and method of manufacture thereof |
| CN102712754A (en) * | 2009-11-20 | 2012-10-03 | E.I.内穆尔杜邦公司 | Coverlay compositions and methods relating thereto |
| CN102918088A (en) * | 2010-03-30 | 2013-02-06 | 可隆工业株式会社 | Polyimide film |
| CN104053724A (en) * | 2012-01-20 | 2014-09-17 | 旭化成电子材料株式会社 | Resin Composition, Layered Product, Multilayered Printed Wiring Board, Multilayered Flexible Wiring Board, And Process For Producing Same |
| CN102627856A (en) * | 2012-04-01 | 2012-08-08 | 云南云天化股份有限公司 | Polyimide film of high-peel-strength flexible printed circuit board, preparation method thereof and printed circuit board made of polyimide film |
| CN104031277A (en) * | 2013-03-07 | 2014-09-10 | 东丽·杜邦股份有限公司 | Polyimide film and manufacturing method thereof |
| CN104774461A (en) * | 2015-04-29 | 2015-07-15 | 江苏亚宝绝缘材料股份有限公司 | Polyimide film prepared through carbonyl dianhydride and diamine |
Non-Patent Citations (3)
| Title |
|---|
| 中国大百科全书出版社编辑部: "《中国大百科全书 化学 1》", 28 February 1989, 中国大百科全书出版社 * |
| 倪文杰: "《简明物资词典》", 30 April 1988, 水利电力出版社 * |
| 朱美芳等: "《中国战略性新兴产业著•新材料 高性能纤维》", 30 November 2017, 中国铁道出版社 * |
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