CN109651631A - A kind of Kapton of low dielectric loss - Google Patents
A kind of Kapton of low dielectric loss Download PDFInfo
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- CN109651631A CN109651631A CN201810047796.4A CN201810047796A CN109651631A CN 109651631 A CN109651631 A CN 109651631A CN 201810047796 A CN201810047796 A CN 201810047796A CN 109651631 A CN109651631 A CN 109651631A
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- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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Abstract
The present invention provides a kind of polyimides, and the Kapton for the ultralow dielectric loss being prepared by the polyimides, and dielectric dissipation factor is 0.0030~0.0060.The polyimides includes general formula (1), structural unit shown in general formula (2) and general formula (3): wherein, 20 moles of % or more of structural unit accounting shown in general formula (1), 20 moles of % or more of structural unit accounting shown in general formula (2), 10 moles of % or more of structural unit accounting shown in general formula (3), the integer that n is 1~10 in general formula (3)；Ar1、Ar2、Ar3For tetravalence aromatic group, Ar4For containing heteroatomic divalent aromatic.Polyimides of the invention is mainly blocked with amido.
Description
Technical field
The present invention relates to a kind of polyimide film materials of low dielectric loss.
Background technique
Kapton (abbreviation PIF) is due to having the heat-resisting, mechanical of brilliance, electric insulation and chemical-resistance, extensively
It is general to be applied to manufacture flexible copper-clad plate, it plays to electronic circuit mechanical support and insulating effect.Dielectric loss value and signal transmit
Directly proportional, common Kapton dielectric loss is lost between 0.020-0.030 or so (10GHz frequency test), and with
Electronics applications frequency improve, frequency spectrum broadens, and to material medium loss, more stringent requirements are proposed, traditional PIF product
It will not be gradually able to satisfy requirement of such product in terms of signal transmission, dielectric loss value is bigger than normal, signal can be hindered to transmit complete
Whole property.Just because of there is such market demand, people have carried out extensive research to low dielectric loss material.
Fluorinated polyimide, it is to introduce fluorine element in diammonium or dianhydride monomer, as polyimides fluorinated volume increases,
The dielectric loss of polyimides drops to 0.010-0.015 or so, and fluorinated polyimide is limited by synthon at present, preparation
Film higher cost, it is important to which the dielectric loss is only the half of traditional polyimide media loss at present, and sexual valence is relatively low.
Liquid crystal polymer (LCP) due to dielectric properties outstanding, in 1~40GHz frequency range dielectric loss because
Number, due to the excellent high frequency characteristics of LCP, solves the severe signal damage that general package substrate occurs in high frequency less than 0.0035
Mistake problem.LCP has caused external great attention as novel high-frequency encapsulating material, but LCP encapsulation technology has been still within
Step section, some critical issues such as metalization layer binding force is not strong, packaging technology is immature and the reliability of encapsulation etc. needs
It solves.
Summary of the invention
The present invention provides a kind of polyimides, and the polyimides of the ultralow dielectric loss prepared by the polyimides is thin
Film.
The polyimides is to polymerize generation with diamine monomer by dianhydride monomer, including general formula (1), general formula (2) and logical
Structural unit shown in formula (3):
Wherein, 20 moles of % or more of structural unit accounting shown in general formula (1), structural unit accounting 20 shown in general formula (2) are rubbed
You are % or more, 10 moles of % or more of structural unit accounting shown in general formula (3), the integer that n is 1~10 in general formula (3)；Ar1、Ar2、
Ar3For tetravalence aromatic group, Ar4For divalent aromatic.
Preferably, Ar1、Ar2、Ar3For the structural unit generated by aromatic series tetracid dianhydride, aromatic series tetracid dianhydride is selected from
3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 2,3,3', 4'- bibenzene tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl ether tetraformic dianhydrides,
2,3,3', 4'- diphenyl ether tetraformic dianhydride, 4,4'- (hexafluoro isopropyl alkene) tetracarboxylic acid dianhydrides, 4,4'- (4,4'- isopropyl diphenyls
Oxygroup) tetracarboxylic acid dianhydride, one of 4,4'- diphenyl sulfone tetracarboxylic acid dianhydrides or a variety of.
Preferably, Ar4 be phenylate type aromatic diamine, be selected from 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ethers,
1,3- bis- (4'- amino-benzene oxygen) benzene, bis- (3'- amino-benzene oxygen) benzene of Isosorbide-5-Nitrae-, 1,3- bis- (3'- amino-benzene oxygen) benzene, 1,3-
Bis- (2- trifluoromethyl-4-aminophenoxyl) benzene, 1,3- bis- (3- trifluoromethyl-4-aminophenoxyl) benzene, 2,2- bis- [4- (4-
Amino-benzene oxygen) phenyl] hexafluoropropane, one of 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane or a variety of, Ar4 is accounted for
Synthesize 20~60 moles of % of the diamines total amount of polyimides described in claim 1.
Preferably, diamine monomer used in structural unit shown in general formula (2) includes having biphenyl two shown in general formula (4)
One or more of amine,
Wherein R1~R8 is separately hydrogen atom, fluorine atom, trifluoromethyl, C1~10Alkyl, C2~4Alkenyl or C1~8Alkane
Oxygroup, and at least one in R1~R8 is not hydrogen atom, and benzidine shown in general formula (4) accounts for described in synthesis claim 1
Polyimides diamines total amount 20~40 moles of %.
Preferably, diamines used in structural unit shown in general formula (3) includes having one of diamines shown in general formula (5)
Or it is a variety of,
Wherein, the integer that n is 1~10, and when n >=3 ,-(CH2)n- it is straight chain or isomers, shown in general formula (5)
Diamines accounts for 10~40 moles of % of the diamines total amount for synthesizing polyimides described in claim 1.
Preferably, the molar ratio for synthesizing diamine monomer used in polyimides of the invention and dianhydride monomer is 1:
(0.990~0.999), the polyimides are mainly blocked with amido.
Preferably, the diamine monomer and dianhydride monomer are that polymerization reaction occurs in a solvent, and the solvent is selected from N-
Methyl pyrrolidone, tetrahydrofuran, toluene, acetone, one of dimethylformamide, dimethyl acetamide or a variety of.
The dielectric dissipation factor of Kapton of the invention is 0.0030~0.0060.
Specific embodiment
The present invention is elaborated below with reference to embodiment, embodiment does not limit the scope of the invention.
One, the synthesis of polyamic acid resin
Embodiment 1.1
In equipped with heating, cooling and interior stirring device 500ml four-neck flask, it is continually fed into nitrogen, excludes air
N-Methyl pyrrolidone 220g is added afterwards and is heated to 60 DEG C, successively puts into the bis- (3- trifluoromethyl -4- ammonia of 1,3- of 0.06mol
Phenoxyl) benzene, the 4,4'- diamino octafluorobiphenyl of 0.03mol and 0.01mol bis- (the 4- amino-benzene oxygens) new penta of 1,3-
Alkane, stirring are completely dissolved above-mentioned diamines.Substep puts into 2,3,3', the 4'- bibenzene tetracarboxylic dianhydride of 0.0995mol, keeps nitrogen
Compression ring border after 60 DEG C of constant temperature are stirred to react 6h, terminate resins synthesis reaction, obtains polyamic acid resin.
Embodiment 1.2
According to the method for embodiment 1.1, wherein 1,3- bis- (3- trifluoromethyl-4-aminophenoxyl) benzene dosage 0.04mol,
1,3- bis- (4- amino-benzene oxygen) neopentane dosage 0.03mol, other conditions remain unchanged, and obtain polyamic acid resin.
Embodiment 1.3
In equipped with heating, cooling and interior stirring device 500ml four-neck flask, it is continually fed into nitrogen, excludes air
N,N-Dimethylformamide 220g is added afterwards and is heated to 80 DEG C, successively puts into the bis- (3- trifluoromethyl -4- of 1,3- of 0.06mol
Amino-benzene oxygen) benzene, the 4,4'- diamino octafluorobiphenyl of 0.03mol and 0.01mol bis- (the 4- amino-benzene oxygens) new penta of 1,3-
Alkane, stirring are completely dissolved above-mentioned diamines.Substep puts into 4,4'- (hexafluoro isopropyl alkene) tetracarboxylic acid dianhydride of 0.0998mol, keeps
Nitrogen environment after 80 DEG C of constant temperature are stirred to react 6h, terminate resins synthesis reaction, obtains polyamic acid resin.
Embodiment 1.4
According to the method for embodiment 1.3, wherein 1,3- bis- (3- trifluoromethyl-4-aminophenoxyl) benzene dosage 0.04mol,
1,3- bis- (4- amino-benzene oxygen) neopentane dosage 0.03mol, other conditions remain unchanged, and obtain polyamic acid resin.
Embodiment 1.5
In equipped with heating, cooling and interior stirring device 500ml four-neck flask, it is continually fed into nitrogen, excludes air
N,N-Dimethylformamide 220g is added afterwards and is heated to 70 DEG C, successively puts into the bis- (3- trifluoromethyl -4- of 1,3- of 0.06mol
Amino-benzene oxygen) benzene, the 4,4'- diamino octafluorobiphenyl of 0.03mol and 0.01mol bis- (the 4- amino-benzene oxygens) new penta of 1,3-
Alkane, stirring are completely dissolved above-mentioned diamines.Substep puts into 4, the 4'- diphenyl sulfone tetracarboxylic acid dianhydride of 0.0995mol, keeps nitrogen
Environment after 80 DEG C of constant temperature are stirred to react 6h, terminate resins synthesis reaction, obtains polyamic acid resin.
Embodiment 1.6
According to the method for embodiment 1.5, wherein 1,3- bis- (3- trifluoromethyl-4-aminophenoxyl) benzene dosage 0.04mol,
1,3- bis- (4- amino-benzene oxygen) neopentane dosage 0.03mol, other conditions remain unchanged, and obtain polyamic acid resin.
Two, the preparation of low dielectric loss Kapton
Embodiment 2.1
It will be coated on mirror face stainless steel plate after the defoaming of the resulting polyamic acid resin of embodiment 1.1, control coating resin
It is about 12 ± 1 μm that solution quantity, which reaches the film thickness finally supported,.Stainless steel is placed in baking oven, heating rate 10
DEG C/min, 390 DEG C are raised to from 60 DEG C.5min is kept after reaching temperature, obtains low dielectric loss Kapton.
Embodiment 2.2
Referring to the method for embodiment 2.1, the resulting polyamic acid resin of embodiment 1.2 is film-made, low dielectric loss is obtained
Film.
Embodiment 2.3
It will be coated on mirror face stainless steel plate after the defoaming of the resulting polyamic acid resin of embodiment 1.3, control coating resin
It is about 12 ± 1 μm that solution quantity, which reaches the film thickness finally supported,.Stainless steel is placed in baking oven, according to film-forming method
(2) it is film-made, heating rate is 10 DEG C/min, is raised to 330 DEG C from 60 DEG C.5min is kept after reaching temperature, obtains low dielectric loss
Kapton.
Embodiment 2.4
Referring to the method for embodiment 2.3, the resulting polyamic acid resin of embodiment 1.4 is film-made, low dielectric loss is obtained
Film.
Embodiment 2.5
It will be coated on mirror face stainless steel plate after the defoaming of the resulting polyamic acid resin of embodiment 1.5, control coating resin
It is about 12 ± 1 μm that solution quantity, which reaches the film thickness finally supported,.Stainless steel is placed in baking oven, according to film-forming method
(3) it is film-made, heating rate is 10 DEG C/min, is raised to 350 DEG C from 60 DEG C.5min is kept after reaching temperature, obtains low dielectric loss
Kapton.
Embodiment 2.6
Referring to the method for embodiment 2.5, the resulting polyamic acid resin of embodiment 1.6 is film-made, low dielectric loss is obtained
Film.
Three, performance detection
The detection of 3.1 tensile strengths and elongation percentage
It is measured according to ASTM D882 standard using tensilon.
The detection of 3.2 dielectric losses
It uses according to ASTM D150 standard and is tested under Network Analyzer 10GHz frequency.
3.3 hydroscopicity
According to the 20 DEG C of immersion 24Hr tests of ASTM D750 standard.
3.4 glass transition temperature
Using dynamic thermomechanical analysis apparatus (TA company, the U.S.): under 1Hz vibration frequency, in a nitrogen atmosphere with 5 DEG C/min
Heating rate be warming up to 450 DEG C, measure glass transition temperature in the maximum value of dielectric loss angle tangent.
3.5 testing result
The survey of the resulting low dielectric loss Kapton of embodiment 2.1~2.6 (film for choosing 12 ± 1 μm of thickness)
Test result is as shown in table 1.
Table 1
| Embodiment 2.1 | Embodiment 2.2 | Embodiment 2.3 | Embodiment 2.4 | Embodiment 2.5 | Embodiment 2.6 | |
| Tensile strength (MPa) | 132 | 105 | 125 | 98 | 145 | 129 |
| Fracture elongation (%) | 22.5 | 13.7 | 30.2 | 15.8 | 44.5 | 28.9 |
| Dielectric dissipation factor | 0.0045 | 0.0034 | 0.0040 | 0.0031 | 0.0049 | 0.0037 |
| Hydroscopicity (%) | 0.82 | 0.65 | 0.45 | 0.36 | 0.77 | 0.55 |
| Glass transition temperature (DEG C) | 335 | 302 | 291 | 270 | 305 | 287 |
The dielectric loss of embodiment 2.2,2.4,2.6 is significantly lower than embodiment 2.1,2.2,2.3 respectively, therefore in polyamides Asia
The quantity that phenylate key is reduced in amine molecule chain, increases the quantity of fat chain structure, advantageously reduces the medium of Kapton
Loss value.
The elongation percentage of embodiment 2.2,2.4,2.6 is significantly lower than embodiment 2.1,2.2,2.3 respectively, therefore it is sub- to increase polyamides
Fat chain structure quantity in amine molecule chain can reduce the elongation percentage of film, change dianhydride structural unit, finally obtain flexibility
Preferable low dielectric loss Kapton.
Low dielectric loss Kapton prepared by the present invention is more suitable for the filming technology of biaxial tension or sizing.Pass through
Biaxial tension or sizing can further improve the elongation percentage of low dielectric loss Kapton.
Kapton of the invention keeping low dielectric loss and under the premise of agent of low hygroscopicity, have excellent toughness and
Heat resistance is suitble to reduce the transmission loss of signal in high-frequency electronic application field.
Claims (7)
1. a kind of polyimides polymerize generation with diamine monomer by dianhydride monomer, which is characterized in that the polyimides includes logical
Structural unit shown in formula (1), general formula (2) and general formula (3):
Wherein, 20 moles of % or more of structural unit accounting shown in general formula (1), 20 moles of % of structural unit accounting shown in general formula (2)
More than, 10 moles of % or more of structural unit accounting shown in general formula (3), the integer that n is 1~10 in general formula (3)；Ar1、Ar2、Ar3For
Tetravalence aromatic group, Ar4For divalent aromatic.
2. polyimides as described in claim 1, which is characterized in that Ar1、Ar2、Ar3It is to be generated by aromatic series tetracid dianhydride
Structural unit, aromatic series tetracid dianhydride be selected from 3,3', 4,4'- bibenzene tetracarboxylic dianhydrides, 2,3,3', 4'- bibenzene tetracarboxylic dianhydride,
3,3', 4,4'- diphenyl ether tetraformic dianhydrides, 2,3,3', 4'- diphenyl ether tetraformic dianhydride, 4,4'- (hexafluoro isopropyl alkene) tetracarboxylic acids
Dianhydride, 4,4'- (4,4'- isopropyl diphenoxy) tetracarboxylic acid dianhydrides, one of 4,4'- diphenyl sulfone tetracarboxylic acid dianhydrides or more
Kind；
Ar4For phenylate type aromatic diamine, it is selected from 4,4'- diaminodiphenyl ether, 3,4'- diaminodiphenyl ethers, 1,3- bis- (4'- ammonia
Phenoxyl) benzene, bis- (3'- amino-benzene oxygen) benzene of Isosorbide-5-Nitrae-, 1,3- bis- (3'- amino-benzene oxygen) benzene, 1,3- bis- (2- fluoroforms
Base -4- amino-benzene oxygen) benzene, 1,3- bis- (3- trifluoromethyl-4-aminophenoxyl) benzene, 2,2- bis- [4- (4- amino-benzene oxygen)
Phenyl] hexafluoropropane, one of 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane or a variety of, Ar4Synthesis right is accounted for want
20~60 moles of % of the diamines total amount of polyimides described in asking 1.
3. polyimides as described in claim 1, which is characterized in that diamines list used in structural unit shown in general formula (2)
Body includes having one or more of benzidine shown in general formula (4),
Wherein R1~R8 is separately hydrogen atom, fluorine atom, trifluoromethyl, C1~10Alkyl, C2~4Alkenyl or C1~8Alkoxy,
And at least one in R1~R8 is not hydrogen atom, and benzidine shown in general formula (4) accounts for synthesis polyamides described in claim 1
20~40 moles of % of the diamines total amount of imines.
4. polyimides as described in claim 1, which is characterized in that diamines packet used in structural unit shown in general formula (3)
It includes with one or more of diamines shown in general formula (5),
Wherein, the integer that n is 1~10, and when n >=3 ,-(CH2)n- it is straight chain or isomers, diamines shown in general formula (5)
Account for 10~40 moles of % of the diamines total amount for synthesizing polyimides described in claim 1.
5. polyimides as described in claim 1, which is characterized in that the molar ratio of the diamine monomer and dianhydride monomer is 1:
(0.990~0.999), the polyimides are mainly blocked with amido.
6. polyimides as described in claim 1, which is characterized in that the diamine monomer is to send out in a solvent with dianhydride monomer
Raw polymerization reaction, the solvent are selected from N-Methyl pyrrolidone, tetrahydrofuran, toluene, acetone, dimethylformamide, dimethyl
One of acetamide is a variety of.
7. a kind of Kapton, which is characterized in that the polyimides as described in claim 1~6 is prepared, medium
Loss factor is 0.0030~0.0060.
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