CN109021265A - A method of preparing the polyimide film of high-modulus low thermal coefficient of expansion - Google Patents
A method of preparing the polyimide film of high-modulus low thermal coefficient of expansion Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a kind of methods of polyimide film for preparing high-modulus low thermal coefficient of expansion, the present invention uses three monomers (pyromellitic acid anhydride PMDA, 4 in Dupont K series and Japanese clock deep pool NPI product, 4 '-diaminodiphenyl ether ODA, p-phenylenediamine PDA) on the basis of further research and develop, ODA is completely or partially replaced with o-tolidine O-Tolidine, the polymerized at room temperature in DMAC solvent, polyamic acid solution is made, film forming is salivated on steel band, and the PI film of high-modulus low thermal coefficient of expansion is made by longitudinal and transverse stretching and hot imidization.With the reduction of ODA dosage, the modulus and mechanical strength of film are increased substantially, and thermal expansion coefficient CTE reduces (hot property is slightly decreased, but does not influence the application of FCCL), and the dimensional stability of film improves.Operation of the present invention is simple, and raw material is easy to get, low in cost, is swift in response, mild condition, is industrializing upper application value with higher.
Description
Technical field
The present invention relates to a kind of methods of polyimide film for preparing high-modulus low thermal coefficient of expansion, are mainly conducive to different lists
When the rigid structure of body and monomer reaction with side-chain structure generate polyimides, nonlinear stiffness structure is formed, reaches and mentions
High-modulus, the purpose for reducing thermal expansion coefficient.
Background technique
Polyimides (PI) film has in wider temperature range and stablizes as high-performance special engineering plastics film
And excellent physical property, chemical property and electrical property, especially there is high fever, cold stability and glass transition temperature,
It is widely used in the high-tech sectors such as space flight and aviation and microelectronics.In the international market, Kapton is mainly used
The substrate of flexibility coat copper plate (FCCL) in H grades, C grades of electric insulations and flexible print wiring board (FPC), the polyamides of FCCL
Imines film, which does not require nothing more than, has the features such as heat resistance possessed by common polyimides is good, chemical stability is good, also requires
Film has the performances such as higher intensity, higher modulus, low heat expansion.
The performance of country's Kapton product (domestic mainstream is prepared using thermal method closed loop) and external commodity at present
The Kapton (foreign countries using chemical catalyst closed loop prepare) of change still has larger gap, be mainly reflected in mechanical performance,
Poor dimensional stability etc..In the manufacture of accurate device, since Kapton is because of poor thermal conductivity or thermal expansion coefficient
The defects of high, so that it is applied to occur in high density and high speed that circuit fever is not easy to dissipate, circuit operating temperature increases phenomenon,
Then the stability for influencing electronic component and integrated circuit and FCCL, even results in electronic circuit and warpage, short circuit, removing occurs
Phenomenon has seriously affected the properties of product of microelectronic circuit, therefore for high-grade FCCL product, it at present can only be big from external import
The chemical method PI film product of amount.
Summary of the invention
For shortcoming and deficiency existing in the prior art, the present invention provides a kind of thermal methods to prepare high-modulus low thermal expansion
The method of the polyimide film of coefficient, it is suitable for high-grade flexible print circuit boards, and operation of the present invention is simple, and raw material is easy to get, at
This is cheap, is swift in response, and reaction condition is mildly industrializing upper application value with higher.
For achieving the above object, the present invention adopts the following technical scheme:
A method of preparing the polyimide film of high-modulus low thermal coefficient of expansion, comprising the following steps: one
1) diamine monomer is dissolved in polar solvent, adds dianhydride, at room temperature, reacted 5-10 hours, close
At highly viscous polyamic acid solution, the molar ratio of diamine monomer and dianhydride is 1:0.9~1；
The dianhydride is pyromellitic acid anhydride PMDA；
The diamine monomer is adjacent connection first diphenylamines O-Tolidine, 4,4 '-diaminodiphenyl ether ODA, p-phenylenediamine
PDA；When a variety of diamine monomers are used in mixed way, by mass percentage, the mass percent of p-phenylenediamine PDA is 10-30%, O-
The mass percent of Tolidine is 10-40%, and residue is mended by ODA to 100%；
2) using dimethyl acetamide DMAC as solvent, above-mentioned highly viscous polyamic acid solution is diluted to low viscosity；
3) by the polyamic acid solution after dilution after vacuum defoaming treatment, time 3-24h；
4) it after coating problems, is put into baking oven by imidization is handled again after ladder-elevating temperature program progress film process；
5) film stripping is obtained into the low-expansion polyimide film of the high-modulus after cooling.
Further, the mass percent of the p-phenylenediamine PDA is 10-25%, the mass percent of O-Tolidine
For 10-30%.
Further, in the step 1), polar solvent be dimethyl acetamide DMAC, dimethylformamide DMF or
MNP.Further, the polar solvent is dimethyl acetamide DMAC.
Further, in the step 2), the solid content of the polyamic acid solution of low viscosity is 15-20%, is glued at 25 DEG C
Degree is 20000~50000cp.About dilution step, in practice it has proved that: (1) from high viscosity be diluted to low viscosity, be conducive to laboratory and
Production line film forming；(2) surface state to form a film is more good-looking than high viscosity film formation surface；(3) levelability adapts to technique requirement, needs to adjust
Viscosity is deacclimatized.
Further, the ladder-elevating temperature program are as follows: heating rate is 5-20 DEG C/min, is started to warm up from 80 DEG C to 120
DEG C constant temperature 1h, is warming up to 200 DEG C of constant temperature 30min, is warming up to 250 DEG C of constant temperature 1h, is warming up to 300 DEG C of constant temperature 30min, and 350 DEG C
10min。
Each material combination is analyzed as follows:
(1) method (acid anhydride is PMDA, and diamines is ODA and PDA) of acid anhydride diamines in the prior art, it is conventional using mixed poly-
Method, two and more than two diamines are added simultaneously, when aggregating into polyimide acid macromolecule resin, molecular chain structure unevenness
It is even, and acid anhydride diamines synthesis is linear polymeric, and from the point of view of CTE, compared to non-linear macromolecule, CTE is wanted
Greatly.O-Tolidine is biphenyl acid anhydride structure, and an ehter bond (flexible bond) has been lacked in centre, and rigidity ratio ODA is stronger, but its flexible ratio
PDA will be got well.With the reduction of ODA dosage, the modulus and mechanical strength of film are increased substantially, and thermal expansion coefficient CTE is reduced, but is adopted
It is poor at gathering than block with the uniformity for mixing poly- method molecular structure, influence various performances.
(2) in an acid anhydride triamine synthetic method of the invention (acid anhydride is PMDA, triamine ODA, O-Tolidine and PDA),
First plus PDA after the reaction was completed, then any order adds other two kinds of diamines to be reacted.The method of the present invention is normal in two-step method preparation
On the basis of advising Kapton, by introducing new monomer, and mole proportion of above-mentioned several raw materials is adjusted, i.e. adjustment rigidity
With the ratio of flexible structure, final obtained high intensity, high-modulus, low CTE Kapton.The new monomer that the present invention selects
For o-tolidine (O-Tolidine), O-Tolidine be with side chain benzidine structure (hot property is slightly decreased, but
The application of FCCL is not influenced), the dimensional stability of film improves, and mechanical performance improves (polymerization of this method bulk and mixed rephasing combination side
The effect of method is got well than an acid anhydride triamine mixes poly- effect).
When more monomers of the invention synthesize, using blocky, mixed poly- method, the performance that can improve product can save again
Equipment and time.The advantages that operation of the present invention is simple, and reaction material is easy to get, low in cost, is swift in response, and reaction condition is mild,
Industrializing upper application value with higher.
(3) it can also form a film if using the method (for an acid anhydride for PMDA, an amine is O-Tolidine) of one amine of an acid anhydride, but modulus
Very high, CTE is low, but elongation at break is low, and film forming is poor, cost is too high, currently without commercial value, is not so good as an above-mentioned acid anhydride two
Amine or triamine.
O-Tolidine is applied in above-mentioned (2) and (3), O-Tolidine has side chain, and the macromolecule of formation is not
Linear polymeric, for the nonlinear macromolecule of side chain, for linear polymeric, CTE is easily made lower.
(4) if using the method (for an acid anhydride for PMDA, an amine is PDA) of one amine of an acid anhydride, i.e., PMDA is reacted with PDA, reaction
Even if material molecular weight obtained is very high, but film it is crisp it is frangible cannot form a film, can not industrialized production.
Specific embodiment
Technical solution of the present invention is described in further detail below by embodiment.The scope of the present invention is not with specific
Embodiment is limited, but is limited by the scope of the claims.
The method of the polyimide film for preparing high-modulus low thermal coefficient of expansion of the present embodiment, below specific steps:
1) diamine monomer is dissolved in polar solvent, adds dianhydride, at room temperature, reacted 5-10 hours, close
At highly viscous polyamic acid solution, the molar ratio of diamine monomer and dianhydride is 1:0.9~1.Diamine monomer is adjacent connection first hexichol
Amine O-Tolidine, p-phenylenediamine PDA, 4,4 '-diaminodiphenyl ether ODA；When a variety of diamine monomers are used in mixed way, by quality hundred
Score meter, the mass percent of p-phenylenediamine PDA are 10-30%, and the mass percent of O-Tolidine is 10-40%, remaining
It is mended by ODA to 100%；Dianhydride is pyromellitic acid anhydride PMDA；Polar solvent is dimethyl acetamide DMAC, dimethyl formyl
Amine DMF or MNP.
Preferably, polar solvent is dimethyl acetamide DMAC.The mass percent of the p-phenylenediamine PDA is 10-
The mass percent of 25%, O-Tolidine are 10-30%.
2) using dimethyl acetamide as solvent, dilution high-viscosity polyamide acid solution to low viscosity, solid content 15-
20%, viscosity is 20000cp--50000cp at 25 DEG C.
3) by the low-viscosity polyamides acid solution after dilution after vacuum defoaming treatment, time 3-24h.
4) resin after defoaming is subjected to film on clean smooth glass plate, be then placed in baking oven by ladder-elevating temperature
Program carries out baking film process.During ladder-elevating temperature, heating rate is 5-20 DEG C/min, is started to warm up from 80 DEG C to 120 DEG C of perseverances
Warm 1h is warming up to 200 DEG C of constant temperature 30min, then removes film from glass plate, after being fixed with fixed frame, is continuously heating to 250
DEG C constant temperature 1h, is warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
5) after cooling, high-strength, high-modulus Kapton is obtained.
Comparative example 1:
It weighs 15.316gODA to be dissolved in 128g DMAC, stirs half an hour under room temperature, be then added portionwise
16.684gPMDA continuously stirs reaction 6h, obtains high-viscosity polyamide acid solution, 40gDMAC is then added, it is suitable to be diluted to
The low viscosity of knifing, solid content 16%.It is filtered and vacuum defoams 3h, then applied on clean smooth glass plate
Film is put into baking oven ladder-elevating temperature, and heating rate is 5 DEG C/min, starts to warm up from 80 DEG C to 120 DEG C of constant temperature 1h, is warming up to 200 DEG C
Then constant temperature 30min removes film from glass plate, after being fixed with fixed frame, be continuously heating to 250 DEG C of constant temperature 1h, be warming up to
300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Comparative example 2:
It weighs 12.817gODA, 1.730gPDA to be dissolved in 128g DMAC, be stirred half an hour under room temperature, then added in batches
Enter 17.452gPMDA, continuously stirs reaction 6h, obtain high-viscosity polyamide acid solution, 40gDMAC is then added, be diluted to suitable
The low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then applied on clean smooth glass plate
Film is put into baking oven ladder-elevating temperature, and heating rate is 5 DEG C/min, starts to warm up from 80 DEG C to 120 DEG C of constant temperature 1h, is warming up to 200 DEG C
Then constant temperature 30min removes film from glass plate, after being fixed with fixed frame, be continuously heating to 250 DEG C of constant temperature 1h, be warming up to
300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Embodiment 1:
Weigh 11.181gODA, 1.725gPDA, 1.693g O-Tolidine are dissolved in 128g DMAC, stirred under room temperature
Mix half an hour, 17.400gPMDA be then added portionwise, continuously stir reaction 6h, obtain high-viscosity polyamide acid solution, then plus
Enter 40gDMAC, is diluted to the low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then completely put down
Film is carried out on whole glass plate, is put into baking oven ladder-elevating temperature, and heating rate is 5 DEG C/min, is started to warm up from 80 DEG C to 120 DEG C
Constant temperature 1h is warming up to 200 DEG C of constant temperature 30min, then removes film from glass plate, after being fixed with fixed frame, is continuously heating to
250 DEG C of constant temperature 1h are warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Embodiment 2:
Weigh 7.939gODA, 1.715gPDA, 5.050g O-Tolidine are dissolved in 128g DMAC, stirred under room temperature
Then 17.296gPMDA is added portionwise in half an hour, continuously stir reaction 6h, obtain high-viscosity polyamide acid solution, be then added
40gDMAC is diluted to the low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then clean smooth
Glass plate on carry out film, be put into baking oven ladder-elevating temperature, heating rate is 5 DEG C/min, is started to warm up from 80 DEG C to 120 DEG C of perseverances
Warm 1h is warming up to 200 DEG C of constant temperature 30min, then removes film from glass plate, after being fixed with fixed frame, is continuously heating to 250
DEG C constant temperature 1h, is warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Embodiment 3:
Weigh 6.415gODA, 2.162gPDA, 5.951g O-Tolidine are dissolved in 128g DMAC, stirred under room temperature
Then 17.469gPMDA is added portionwise in half an hour, continuously stir reaction 6h, obtain high-viscosity polyamide acid solution, be then added
40gDMAC is diluted to the low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then clean smooth
Glass plate on carry out film, be put into baking oven ladder-elevating temperature, heating rate is 5 DEG C/min, is started to warm up from 80 DEG C to 120 DEG C of perseverances
Warm 1h is warming up to 200 DEG C of constant temperature 30min, then removes film from glass plate, after being fixed with fixed frame, is continuously heating to 250
DEG C constant temperature 1h, is warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Embodiment 4:
Weigh 9.555gODA, 1.72gPDA, 3.377g O-Tolidine are dissolved in 128g DMAC, stirred under room temperature
Then 17.348gPMDA is added portionwise in half an hour, continuously stir reaction 6h, obtain high-viscosity polyamide acid solution, be then added
40gDMAC is diluted to the low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then clean smooth
Glass plate on carry out film, be put into baking oven ladder-elevating temperature, heating rate is 5 DEG C/min, is started to warm up from 80 DEG C to 120 DEG C of perseverances
Warm 1h is warming up to 200 DEG C of constant temperature 30min, then removes film from glass plate, after being fixed with fixed frame, is continuously heating to 250
DEG C constant temperature 1h, is warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Embodiment 5:
Weigh 9.085gODA, 6.421g O-Tolidine is dissolved in 128g DMAC, stirred half an hour under room temperature, so
After 16.494gPMDA is added portionwise, continuously stir reaction 6h, obtain high-viscosity polyamide acid solution, 40gDMAC be then added,
It is diluted to the low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then in clean smooth glass plate
Upper carry out film is put into baking oven ladder-elevating temperature, and heating rate is 5 DEG C/min, starts to warm up from 80 DEG C to 120 DEG C of constant temperature 1h, rises
Then film is removed from glass plate to 200 DEG C of constant temperature 30min, after being fixed with fixed frame, is continuously heating to 250 DEG C of constant temperature by temperature
1h is warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
Embodiment 6:
Weigh 10.629gODA, 4.830g O-Tolidine is dissolved in 128g DMAC, stirred half an hour under room temperature, so
After 16.541gPMDA is added portionwise, continuously stir reaction 6h, obtain high-viscosity polyamide acid solution, 40gDMAC be then added,
It is diluted to the low viscosity of suitable knifing, solid content 16%.It is filtered and vacuum defoams 3h, then in clean smooth glass plate
Upper carry out film is put into baking oven ladder-elevating temperature, and heating rate is 5 DEG C/min, starts to warm up from 80 DEG C to 120 DEG C of constant temperature 1h, rises
Then film is removed from glass plate to 200 DEG C of constant temperature 30min, after being fixed with fixed frame, is continuously heating to 250 DEG C of constant temperature by temperature
1h is warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
PI thin film data analysis obtained in 1 comparative example of table and embodiment
| Sample | Thickness/um | Tensile strength/MPa | Elasticity modulus/MPa |
| Comparative example 1 | 25 | 140-160 | 2400-2600 |
| Comparative example 2 | 25.1 | 150-170 | 3200-3400 |
| Embodiment 1 | 24.9 | 160-180 | 3800-4200 |
| Embodiment 2 | 24.8 | 170-200 | 5500-5800 |
| Embodiment 3 | 25.1 | 190-210 | 5900-6100 |
| Embodiment 4 | 25.1 | 170-190 | 4100-4300 |
| Embodiment 5 | 24.8 | 170-190 | 4300-4500 |
| Embodiment 6 | 25 | 160-180 | 3900-4200 |
The tensile strength and elasticity modulus of embodiment 1-6 is laboratory test results, and laboratory is not due to having double stretching survey
Equipment is tried, routinely film shows that mechanical performance is relatively low compared with industrializing film in laboratory；In actual industrial production, by one
The combination of acid anhydride Triamine monomer and content are different, and at least between 170~260Mpa, elasticity modulus reaches as high as tensile strength
6.5Gpa。
It should be understood that above-described embodiment is only one of the preferred embodiment of the present invention, for illustrating technical solution of the present invention
Specific embodiment, rather than limit the scope of the invention.It is noted that, after the present invention has been read, art technology
Personnel without departing from the principle of the present invention, can also make several improvement, such as mix poly- method and be changed to blocky gather
It closes, thermal method closed loop changes chemical method closed loop, and the various performances of film will be more preferable, these modifications to various equivalent forms of the invention
Protection scope defined by the claim of this application is fallen with replacement.
Claims (6)
1. a kind of method for the polyimide film for preparing high-modulus low thermal coefficient of expansion, which comprises the following steps:
1) diamine monomer is dissolved in polar solvent, adds dianhydride, at room temperature, reacted 5-10 hours, synthesis is high
The molar ratio of viscosity, high molecular polyamic acid solution, diamine monomer and dianhydride is 1:0.9~1；
The dianhydride is pyromellitic acid anhydride PMDA；The diamine monomer is adjacent connection first diphenylamines O-Tolidine, 4,4 '-two
Amido diphenyl ether ODA, p-phenylenediamine PDA；When a variety of diamine monomers are used in mixed way, by mass percentage, p-phenylenediamine PDA's
Mass percent is 10-30%, and the mass percent of O-Tolidine is 10-40%, and residue is mended by ODA to 100%；
2) using dimethyl acetamide DMAC as solvent, above-mentioned highly viscous polyamic acid solution is diluted to low viscosity；
3) by the polyamic acid solution after dilution after vacuum defoaming treatment, time 3-24h；
4) it after coating problems, is put into baking oven by imidization is handled again after ladder-elevating temperature program progress film process；
5) film stripping is obtained into the low-expansion polyimide film of the high-modulus after cooling.
2. a kind of method for the polyimide film for preparing high-modulus low thermal coefficient of expansion as described in claim 1, feature exist
In the mass percent of the p-phenylenediamine PDA is 10-25%, and the mass percent of O-Tolidine is 10-30%.
3. a kind of method for the polyimide film for preparing high-modulus low thermal coefficient of expansion as claimed in claim 1 or 2, feature
It is, in the step 1), polar solvent is dimethyl acetamide DMAC, dimethylformamide DMF or MNP.
4. a kind of method for the polyimide film for preparing high-modulus low thermal coefficient of expansion as claimed in claim 3, feature exist
In the polar solvent is dimethyl acetamide DMAC.
5. a kind of method for the polyimide film for preparing high-modulus low thermal coefficient of expansion as claimed in claim 1 or 2, feature
Be, in the step 2), the solid content of the polyamic acid solution of low viscosity is 15-20%, at 25 DEG C viscosity be 20000~
50000cp。
6. a kind of method for the polyimide film for preparing high-modulus low thermal coefficient of expansion as claimed in claim 1 or 2, feature
It is, the ladder-elevating temperature program are as follows: heating rate is 5-20 DEG C/min, is started to warm up from 80 DEG C to 120 DEG C of constant temperature 1h, heating
To 200 DEG C of constant temperature 30min, 250 DEG C of constant temperature 1h are warming up to, are warming up to 300 DEG C of constant temperature 30min, 350 DEG C of 10min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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