CN106543720A - A kind of Kapton of low thermal coefficient of expansion and preparation method thereof - Google Patents
A kind of Kapton of low thermal coefficient of expansion and preparation method thereof Download PDFInfo
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- CN106543720A CN106543720A CN201610954820.3A CN201610954820A CN106543720A CN 106543720 A CN106543720 A CN 106543720A CN 201610954820 A CN201610954820 A CN 201610954820A CN 106543720 A CN106543720 A CN 106543720A
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention belongs to polymeric material field, is specifically related to a kind of Kapton of low thermal coefficient of expansion and preparation method thereof.The Kapton has following structural formula：Wherein, R1 and R3 are the residues of two kinds of different tetracarboxylic dianhydride's monomers, and R2 is two kinds of different binary primary amine monomers with R4.Its preparation method is multistep polymerization method, and polymerization obtains two kinds of polyimides acid solutions with different structure unit respectively first, is then mixed repolymerization, and finally heated dried obtains the Kapton of low thermal coefficient of expansion.Compared with prior art, the Kapton of the low thermal coefficient of expansion that the present invention is provided introduces the construction units such as ester bond/amide, Mi Zuo/oxazoles in Molecular Design simultaneously, improve intermolecular interaction force, effectively reduce the thermal coefficient of expansion of Kapton, different formula is adopted simultaneously, its thermal coefficient of expansion can be regulated and controled, solve the matching problem between different base materials.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of low thermal coefficient of expansion Kapton and its
Preparation method.
Background technology
Polyimides are topmost kinds in the aromatic heterocyclic copolymer for growing up nearly half a century, and using temperature
Degree one family macromolecule material of highest, with the synthesis that high mechanical strength, high temperature resistant, chemically stable, creep resistant etc. are very excellent
Performance, is widely used at the aspect such as Aeronautics and Astronautics, electric, machinery, microelectronics, chemical industry.
But polyimides have larger thermal coefficient of expansion (40-80 × 10-6/ K), this greatly limits which and apply model
Enclose, especially the application in microelectronic industry, such as in above-mentioned encapsulated circuit, polyimides and conductive material or substrate
Thermal coefficient of expansion has very big difference, and (thermal coefficient of expansion such as Cu is 16-18 × 10-6/ K, SiO2Thermal coefficient of expansion be 14
×10-6/ K, Si thermal coefficient of expansion is 3-6 × 10-6/ K), serious thermal coefficient of expansion is mismatched can cause encapsulating material in encapsulation
Layering or cracking during the heat treatment of process or encapsulated circuit use, even results in the failure of material or device.Therefore,
The thermal coefficient of expansion of polyimides is reduced, is allowed to the conductive layer in encapsulated circuit with preferably thermally matched with important meaning
Justice.
The content of the invention
The purpose of the present invention is to overcome above-mentioned deficiency of the prior art, there is provided a kind of polyimides of low thermal coefficient of expansion
Thin film and preparation method thereof.
The present invention overcomes the technical scheme that the deficiencies in the prior art are adopted as follows：A kind of polyimides of low thermal coefficient of expansion
Thin film, the structural formula of the polyimides are as follows：
Wherein, R1 and R3 are the residues of two kinds of different tetracarboxylic dianhydride's monomers, and R2 is two kinds of different binary primary with R4
The residue of amine monomers, m and n are the integer more than zero.
Specifically, described R4 is one or more in following three kinds of groups：
Described R1 be the following two kinds group in one or two:
Described R2 is one or more in following three kinds of groups:
Described R3 be the following two kinds group in one or two：
Optimal, described R4 is preferably one or two in the following two kinds group：
Optimal, described R2 is preferably one or two in the following two kinds group：.
Optimal, described R3 is preferably following group：
Present invention also offers the preparation method of the Kapton of the above-mentioned low thermal coefficient of expansion stated, which includes as follows
Step：
S1., under nitrogen protection, the first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer and organic solvent are added
To in consersion unit, it is stirred at room temperature, prepares sticky polyamide solution A, it is standby；
S2., under nitrogen protection, second tetracarboxylic dianhydride's monomer, second binary primary amine monomer and organic solvent are added
In consersion unit, it is stirred at room temperature, prepares sticky polyamic acid solution B, it is standby；
S3. the polyamic acid solution B in polyamide solution A and S2 in S1 is mixed, is stirred at room temperature, prepared most
Whole polyamic acid solution；
S4. the polyamic acid solution of S3 is diluted and the solution after dilution is coated uniformly on the tape casting the glass of cleaning
On plate, heat drying process obtains final product the Kapton of described low thermal coefficient of expansion.
Wherein, the first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer, second tetracarboxylic dianhydride's monomer and
The mol ratio of two kinds of binary primary amine monomers is (0.1-0.6):(0.1-0.6):(0.4-0.9):(0.4-0.9).
Preferably, the first described tetracarboxylic dianhydride's monomer adopts pyromellitic acid anhydride and 3,3', 4,4'- biphenyl four
One or two in carboxylic acid dianhydride, the first binary primary amine monomer adopt 4,4'- DADPSs, 4,4 '-diaminourea connection
One or more in benzene and p-phenylenediamine, second tetracarboxylic dianhydride is using in benzene diester dianhydride and terephthalate amine dianhydride
One or two, second binary primary amine monomer adopts 2- (4- aminophenyls) -6- aminobenzimidazoles, 2- (4- aminobenzenes
Base) one or more in -6- An bases benzoxazoles and 2- (5- aminophenyls) -6- An base benzoxazoles.
Specifically, the solvent adopted when being diluted to the polyamic acid solution of S3 in S4 is N-Methyl pyrrolidone or N,
N- dimethyl acetylamide.
Specifically, in S4, the particular content of heat drying process is：Glass plate is positioned over into 0.5- in 80 DEG C of drying baker
1h, is warming up to 150 DEG C, is dried 0.5-1h, is warming up to 200 DEG C, is dried 0.5-1h, is warming up to 250 DEG C, is dried 0.5-1h, heats up
To 300 DEG C, 0.5-1h is dried, glass plate is taken out after temperature is down to 25 DEG C, be placed on demoulding in water, then thin film is placed in
Eliminating water is dried in 100 DEG C of drying baker, Kapton is obtained, then by the Kapton under the conditions of 300-400 DEG C
Heat treatment 0.5-1h.
Compared with prior art, the Kapton of the low thermal coefficient of expansion that the present invention is provided is in Molecular Design
The construction units such as ester bond/amide, Mi Zuo/oxazoles are introduced simultaneously, intermolecular interaction force is improved, and improve the orderly of strand
Arrangement, adopts the method for multistep copolymerization in the preparation process of Kapton resin, realizes reducing Kapton
Thermal coefficient of expansion.Different formula is adopted simultaneously, the thermal coefficient of expansion of Kapton can be entered between 0-15ppm/K
Row regulation and control, to solve the matching problem of different base materials.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and example is served only for explaining this
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 4.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, 4.0mmol 4,4 '-diamino
Base biphenyl, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid molten
Liquid A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 4.0mmol, 2- (4- the aminophenyls) -6- ammonia of 4.0mmol
Base benzimidazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.Wherein film drying
Process as follows：Glass plate is positioned over 1 hour in 80 DEG C of drying baker, 150 DEG C are warming up to, 0.5-1 hours is dried, is warming up to
200 DEG C, 0.5-1 hours are dried, are warming up to 250 DEG C, be dried 0.5-1 hours, be warming up to 300 DEG C, be dried 0.5-1 hours, treat temperature
Degree takes out glass plate after being down to 25 DEG C, is placed on demoulding in water, then thin film is placed in 100 DEG C of drying baker and is dried eliminating water,
Obtain Kapton, then by the Kapton under the conditions of 300-400 DEG C heat treatment 0.5-1 hours, obtain low
The Kapton of thermal coefficient of expansion.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 383 DEG C, 5% heat decomposition temperature is 530
DEG C, thermal coefficient of expansion CTE is 7ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 160MPa, and stretch moduluses are 5GPa,
Elongation at break is 45%.Mechanical performance is excellent.
Embodiment 2：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 2.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, 4.0mmol 4,4 '-diamino
Base biphenyl, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid molten
Liquid A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- the aminophenyls) -6- ammonia of 4.0mmol
Base benzimidazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), Kapton is obtained according to film drying processing method in embodiment 1.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 375 DEG C, 5% heat decomposition temperature is 530
DEG C, thermal coefficient of expansion CTE is 8ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 151MPa, and stretch moduluses are
4.6GPa, elongation at break are 52%.Mechanical performance is excellent.
Embodiment 3：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 1.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, 3.0mmol 4,4 '-diamino
Base biphenyl, 10 milliliters of N,N-dimethylacetamide are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 7.0mmol, 2- (4- the aminophenyls) -6- ammonia of 5.0mmol
Base benzimidazole, 20 milliliters of N,N-dimethylacetamide are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamides
Amino acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 380 DEG C, 5% heat decomposition temperature is 540
DEG C, thermal coefficient of expansion CTE is 8ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.03% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 153MPa, and stretch moduluses are 4GPa,
Elongation at break is 64%.Mechanical performance is excellent.
Embodiment 4：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 3.0mmol 4,4 '-benzidine, 10
Milliliter N-Methyl pyrrolidone is added in reaction bulb, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- the aminophenyls) -6- ammonia of 5.0mmol
Base benzoxazole, 20 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 400 DEG C, 5% heat decomposition temperature is 560
DEG C, thermal coefficient of expansion CTE is 7ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.01% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 200MPa, and stretch moduluses are
5.3GPa, elongation at break are 38%.Mechanical performance is excellent.
Embodiment 5：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 3.0mmol 4,4 '-benzidine, 10
Milliliter N,N-dimethylacetamide is added in reaction bulb, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- the aminophenyls) -6- ammonia of 5.0mmol
Base benzimidazole, 20 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4) it is 10% that the polyamic acid solution DMAC N,N' dimethyl acetamide of preparation is configured to concentration expressed in percentage by weight,
Solution, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According to embodiment 1
Middle film drying processing method obtains Kapton.Obtain the Kapton of low thermal coefficient of expansion.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 408 DEG C, 5% heat decomposition temperature is 556
DEG C, thermal coefficient of expansion CTE is 9ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 203MPa, and stretch moduluses are
5.6GPa, elongation at break are 40%.Mechanical performance is excellent.
Embodiment 6：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 3.0mmol 4,4 '-benzidine, 10
Milliliter N-Methyl pyrrolidone is added in reaction bulb, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by 6.0mmol to benzene diester dianhydride, 2- (4- the aminophenyls) -6- amino of 5.0mmol
Benzimidazole, 20 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 363 DEG C, 5% heat decomposition temperature is 552
DEG C, thermal coefficient of expansion CTE is 10ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 160MPa, and stretch moduluses are
4.6GPa, elongation at break are 80%.Mechanical performance is excellent.
Embodiment 7：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 3.0mmol 4,4 '-benzidine, 10
Milliliter N-Methyl pyrrolidone is added in reaction bulb, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by 6.0mmol to benzene diester dianhydride, 2- (4- the aminophenyls) -6- amino of 5.0mmol
Benzoxazole, 20 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 368 DEG C, 5% heat decomposition temperature is 540
DEG C, thermal coefficient of expansion CTE is 6ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 158MPa, and stretch moduluses are
4.8GPa, elongation at break are 75%.Mechanical performance is excellent.
Embodiment 8：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 2.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, 4.0mmol 4,4 '-diamino
Base biphenyl, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid molten
Liquid A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- the aminophenyls) -6- ammonia of 4.0mmol
Base benzoxazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 420 DEG C, 5% heat decomposition temperature is 575
DEG C, thermal coefficient of expansion CTE is 5ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 202MPa, and stretch moduluses are 6GPa,
Elongation at break is 70%.Mechanical performance is excellent.
Embodiment 9：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 2.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, 4.0mmol 4,4 '-diamino
Base biphenyl, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid molten
Liquid A；
(2), under nitrogen protection, by 6.0mmol to benzene diester dianhydride, 2- (4- the aminophenyls) -6- amino of 4.0mmol
Benzimidazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 390 DEG C, 5% heat decomposition temperature is 563
DEG C, thermal coefficient of expansion CTE is 6ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.01% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 156MPa, and stretch moduluses are 4GPa,
Elongation at break is 67%.Mechanical performance is excellent.
Embodiment 10：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 2.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, 4.0mmol 4,4 '-diamino
Base biphenyl, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid molten
Liquid A；
(2), under nitrogen protection, by 6.0mmol to benzene diester dianhydride, 2- (4- the aminophenyls) -6- amino of 4.0mmol
Benzoxazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 386 DEG C, 5% heat decomposition temperature is 552
DEG C, thermal coefficient of expansion CTE is 5ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 157MPa, and stretch moduluses are
4.8GPa, elongation at break are 58%.Mechanical performance is excellent.
Embodiment 11：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 4.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, the p-phenylenediamine of 4.0mmol,
15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, prepare sticky polyamic acid solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 4.0mmol, 2- (4- the aminophenyls) -6- ammonia of 4.0mmol
Base benzimidazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 420 DEG C, 5% heat decomposition temperature is 580
DEG C, thermal coefficient of expansion CTE is 6ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.01% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 220MPa, and stretch moduluses are 8GPa,
Elongation at break is 58%.Mechanical performance is excellent.
Embodiment 12：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 4.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, the p-phenylenediamine of 4.0mmol,
15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, prepare sticky polyamic acid solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 4.0mmol, 2- (4- the aminophenyls) -6- ammonia of 4.0mmol
Base benzoxazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 412 DEG C, 5% heat decomposition temperature is 578
DEG C, thermal coefficient of expansion CTE is 4ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.03% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 210MPa, and stretch moduluses are 7GPa,
Elongation at break is 60%.Mechanical performance is excellent.
Embodiment 13：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 4.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, the p-phenylenediamine of 4.0mmol,
15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, prepare sticky polyamic acid solution A；
(2), under nitrogen protection, by 4.0mmol to benzene diester dianhydride, 2- (4- the aminophenyls) -6- amino of 4.0mmol
Benzoxazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 391 DEG C, 5% heat decomposition temperature is 550
DEG C, thermal coefficient of expansion CTE is 4ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 155MPa, and stretch moduluses are
4.8GPa, elongation at break are 60%.Mechanical performance is excellent.
Embodiment 14：
In the present embodiment, polyimide resin material has following structural formula：
Specifically preparation method is：
(1), nitrogen protection under, by the 3,3' of 4.0mmol, 4,4'- biphenyl tetracarboxylic dianhydrides, the p-phenylenediamine of 4.0mmol,
15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, prepare sticky polyamic acid solution A；
(2), under nitrogen protection, by 4.0mmol to benzene diester dianhydride, 2- (4- the aminophenyls) -6- amino of 4.0mmol
Benzimidazole, 15 milliliters of N-Methyl pyrrolidone are added in reaction bulb, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, is prepared final
Polyamic acid solution；
(4), by the polyamic acid solution N-Methyl pyrrolidone of preparation be configured to concentration expressed in percentage by weight be 10% it is molten
Liquid, is coated uniformly on solution on the glass plate of cleaning with the tape casting, and solution coating thickness is 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Carry out test and obtain for the hot property of thin film, glass transition temperature is 382 DEG C, 5% heat decomposition temperature is 546
DEG C, thermal coefficient of expansion CTE is 5ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.06% (200 DEG C, 2 hours).Possess hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of thin film：Tensile strength is 180MPa, and stretch moduluses are
5.3GPa, elongation at break are 45%.Mechanical performance is excellent.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. a kind of Kapton of low thermal coefficient of expansion, it is characterised in that the structural formula of the polyimides is as follows：
Wherein, R1 and R3 are the residues of two kinds of different tetracarboxylic dianhydride's monomers, and R2 is two kinds of different binary primary amine lists with R4
The residue of body, m and n are the integer more than zero.
2. the Kapton of a kind of low thermal coefficient of expansion according to claim 1, it is characterised in that described R4 is
One or more in following three kinds of groups：
3. the Kapton of a kind of low thermal coefficient of expansion according to claim 2, it is characterised in that described R1 is
One or two in the following two kinds group:
Described R2 is one or more in following three kinds of groups:
Described R3 be the following two kinds group in one or two：
4. the Kapton of a kind of low thermal coefficient of expansion according to claim 2, it is characterised in that described R4 is
One or two in the following two kinds group：
5. the Kapton of a kind of low thermal coefficient of expansion according to right wants 4, it is characterised in that described R2 be as
One or two in lower two kinds of groups：.
Described R3 is following group：
6. a kind of preparation method of the Kapton of the low thermal coefficient of expansion as described in any one of claim 1 to 5, which is special
Levy and be, comprise the steps：
S1., under nitrogen protection, the first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer and organic solvent are added to instead
In answering equipment, it is stirred at room temperature, prepares sticky polyamide solution A, it is standby；
S2., under nitrogen protection, second tetracarboxylic dianhydride's monomer, second binary primary amine monomer and organic solvent are added and is reacted
In equipment, it is stirred at room temperature, prepares sticky polyamic acid solution B, it is standby；
S3. the polyamic acid solution B in polyamide solution A and S2 in S1 is mixed, is stirred at room temperature, prepared final
Polyamic acid solution；
S4. the polyamic acid solution of S3 is diluted and the solution after dilution is coated uniformly on the tape casting the glass plate of cleaning
On, heat drying process obtains final product the Kapton of described low thermal coefficient of expansion.
7. the preparation method of the Kapton of a kind of low thermal coefficient of expansion according to claim 6, it is characterised in that
The first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer, second tetracarboxylic dianhydride's monomer and second binary primary amine
The mol ratio of monomer is (0.1-0.6):(0.1-0.6):(0.4-0.9):(0.4-0.9).
8. the preparation method of the Kapton of a kind of low thermal coefficient of expansion according to claim 6, it is characterised in that
The first described tetracarboxylic dianhydride monomer is using in pyromellitic acid anhydride and 3,3', 4,4'- biphenyl tetracarboxylic dianhydride
Kind or two kinds, the first binary primary amine monomer adopt 4,4'- DADPSs, 4, in 4 '-benzidine and p-phenylenediamine
One or more, second tetracarboxylic dianhydride using to one or two in benzene diester dianhydride and terephthalate amine dianhydride,
Second binary primary amine monomer adopts 2- (4- aminophenyls) -6- aminobenzimidazoles, 2- (4- aminophenyls) -6- amino benzos
One or more in oxazole and 2- (5- aminophenyls) -6- An base benzoxazoles.
9. the preparation method of the Kapton of a kind of low thermal coefficient of expansion according to claim 6 to 8, its feature exist
In the solvent adopted when being diluted to the polyamic acid solution of S3 in S4 is N-Methyl pyrrolidone or N, N- dimethylacetamide
Amine.
10. a kind of preparation method of the Kapton of low thermal coefficient of expansion according to any one of claim 6 to 8, its
It is characterised by, the particular content that heat drying is processed in S4 is：Glass plate is positioned over into 0.5-1h in 80 DEG C of drying baker, is heated up
To 150 DEG C, 0.5-1h is dried, is warming up to 200 DEG C, is dried 0.5-1h, be warming up to 250 DEG C, be dried 0.5-1h, be warming up to 300 DEG C,
0.5-1h is dried, glass plate is taken out after temperature is down to 25 DEG C, is placed on demoulding in water, thin film is placed in into 100 DEG C then and is done
Eliminating water is dried in dry case, Kapton is obtained, then by the Kapton under the conditions of 300-400 DEG C heat treatment
0.5-1h。
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928481A (en) * | 2017-04-06 | 2017-07-07 | 上海交通大学 | The optimization preparation method of Kapton |
| CN107556501A (en) * | 2017-08-23 | 2018-01-09 | 中国科学院理化技术研究所 | Polyimide film and preparation method and application thereof |
| CN109721749A (en) * | 2018-12-14 | 2019-05-07 | 上海市合成树脂研究所有限公司 | A kind of thermostable type Kapton and preparation method containing heteroaromatic |
| CN109817852A (en) * | 2018-12-29 | 2019-05-28 | 武汉依麦德新材料科技有限责任公司 | A kind of lithium ion battery outer cover material and preparation method thereof |
| CN109897180A (en) * | 2017-12-08 | 2019-06-18 | 株式会社斗山 | Polyamic acid solution, clear polyimides resin film and transparent substrate using it |
| CN110372896A (en) * | 2019-06-20 | 2019-10-25 | 重庆文理学院 | A kind of heat treatment process of low thermal expansion coefficient polyimide |
| CN111484615A (en) * | 2020-05-11 | 2020-08-04 | 浙江中科玖源新材料有限公司 | Transparent polyimide film with low thermal expansion coefficient and water absorption and preparation method thereof |
| CN112457493A (en) * | 2020-11-30 | 2021-03-09 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
| CN112876680A (en) * | 2021-02-04 | 2021-06-01 | 武汉柔显科技股份有限公司 | Polyamide acid slurry, preparation method thereof and polyimide film |
| JP7183377B1 (en) | 2021-11-26 | 2022-12-05 | 住友化学株式会社 | polyimide resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558860A (en) * | 2011-12-22 | 2012-07-11 | 桂林电器科学研究院 | Dimensionally-stable polyimide film and preparation method thereof |
| CN105330860A (en) * | 2015-12-01 | 2016-02-17 | 常州市尚科特种高分子材料有限公司 | Thermoplastic polyimide resin powder and preparation method thereof |
-
2016
- 2016-10-27 CN CN201610954820.3A patent/CN106543720B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558860A (en) * | 2011-12-22 | 2012-07-11 | 桂林电器科学研究院 | Dimensionally-stable polyimide film and preparation method thereof |
| CN105330860A (en) * | 2015-12-01 | 2016-02-17 | 常州市尚科特种高分子材料有限公司 | Thermoplastic polyimide resin powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MASATOSHI HASEGAWA ET AL.,: "High-temperature polymers overcoming the trade-off between excellent thermoplasticity and low thermal expansion properties", 《POLYMER》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106928481A (en) * | 2017-04-06 | 2017-07-07 | 上海交通大学 | The optimization preparation method of Kapton |
| CN107556501A (en) * | 2017-08-23 | 2018-01-09 | 中国科学院理化技术研究所 | Polyimide film and preparation method and application thereof |
| CN109897180A (en) * | 2017-12-08 | 2019-06-18 | 株式会社斗山 | Polyamic acid solution, clear polyimides resin film and transparent substrate using it |
| CN109897180B (en) * | 2017-12-08 | 2021-08-03 | 株式会社斗山 | Polyamide acid solution, transparent polyimide resin film using same, and transparent substrate |
| CN109721749A (en) * | 2018-12-14 | 2019-05-07 | 上海市合成树脂研究所有限公司 | A kind of thermostable type Kapton and preparation method containing heteroaromatic |
| CN109817852A (en) * | 2018-12-29 | 2019-05-28 | 武汉依麦德新材料科技有限责任公司 | A kind of lithium ion battery outer cover material and preparation method thereof |
| CN110372896A (en) * | 2019-06-20 | 2019-10-25 | 重庆文理学院 | A kind of heat treatment process of low thermal expansion coefficient polyimide |
| CN111484615A (en) * | 2020-05-11 | 2020-08-04 | 浙江中科玖源新材料有限公司 | Transparent polyimide film with low thermal expansion coefficient and water absorption and preparation method thereof |
| CN112457493A (en) * | 2020-11-30 | 2021-03-09 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
| CN112876680A (en) * | 2021-02-04 | 2021-06-01 | 武汉柔显科技股份有限公司 | Polyamide acid slurry, preparation method thereof and polyimide film |
| JP7183377B1 (en) | 2021-11-26 | 2022-12-05 | 住友化学株式会社 | polyimide resin |
| JP2023079092A (en) * | 2021-11-26 | 2023-06-07 | 住友化学株式会社 | polyimide resin |
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Effective date of registration: 20221114 Address after: 412,000 Room 101, Building E1, Scientific Innovation Industrial Park, Nanzhou Town, Lukou District, Zhuzhou City, Hunan Province Patentee after: Zhuzhou Tianyilai New Material Technology Co.,Ltd. Address before: Building 39, Unit 701, 7/F, Building 4, North Area A5, Future Science and Technology City, No. 999, High tech Avenue, Donghu Hi tech Development Zone, Wuhan, Hubei 430070 Patentee before: WUHAN YIMAIDE NEW MATERIALS TECHNOLOGY Co.,Ltd. |