CN1872895A - Dissoluble polyimide resin, and preparation method - Google Patents
Dissoluble polyimide resin, and preparation method Download PDFInfo
- Publication number
- CN1872895A CN1872895A CN 200510074874 CN200510074874A CN1872895A CN 1872895 A CN1872895 A CN 1872895A CN 200510074874 CN200510074874 CN 200510074874 CN 200510074874 A CN200510074874 A CN 200510074874A CN 1872895 A CN1872895 A CN 1872895A
- Authority
- CN
- China
- Prior art keywords
- polyimide resin
- monomer
- dianhydride monomer
- resin
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
This invention provides a method for preparing a polyimide resin. The method comprises: (1) polymerizing dianhydride monomer and diamine monomer to obtain polyamic acid resin; (2) imidizing to obtain the polyimide resin. The chemical formulae of the two monomers are shown in formulae I and II, respectively. In formula I, R is O or -O (CH2)nO-, and n is an integer among 0-2. The polyimide resin has such advantages as improved water absorbency, low thermal expansion coefficient, good thermal resistance and high size stability.
Description
Technical field
The invention relates to a kind of polyimide resin and method for making thereof, particularly about a kind of polyimide resin and method for making thereof with solubility.
Background technology
Because the slimming of electronic and communication facility and the requirement of microminiaturization, the integrated circuit package body in the equipment is long-pending also to be developed to microminiaturization and slimming in recent years, the circuit of the employed wired circuit board granular that becomes that also heals.In various wired circuit boards, flexible printed wiring board can significantly reduce the volume and the weight of electronic component, is a kind of wired circuit board commonly used.
Usually the structure of flexible printed wiring board comprises insulating substrate and metal conductor layer, and insulating substrate and metal conductor layer with the bonding formation circuit of tackiness agent laminated plates, are used the material of Copper Foil as metal level usually.Polyimide resin has thermotolerance, chemical resistance, excellent mechanical properties and good electrical properties, is a kind of insulating substrate material commonly used.Metal level engages employed tackiness agent and is generally Resins, epoxy or acryl resin solid with insulating substrate.Yet the thermotolerance of these tackiness agents is not good, breaks easily in follow-up resin heat embrittlement making processes, reduces the flexible printed wiring board size stability.For head it off, the someone attempts rubber elastomer added in the tackiness agent avoiding breaks.But the thermostability of rubber elastomer is not good, and meeting deterioration in high temperature process causes the physical properties of flexible circuit board to reduce.
The characteristic of polyimide resin layer also can influence the quality of laminated plates, when polyimide resin contains more amide group, can increase the water-absorbent of polyimide resin layer, can make amide group be decomposed into imido grpup and acidic group.Importing other functional group at molecular backbone chain can allow the polyimide resin water-intake rate reduce.But the too many monomeric application of long-chain meeting causes the polyimide resin layer flexibility decrease, and the linear expansivity increase causes prepared laminated plates dimensional change big, and dimensional stability reduces.
In addition, the polyimide acid resin can't be dissolved in organic solvent usually, thereby significantly reduce its applicability after the dehydration endless loop.Therefore, need a kind ofly can reduce water-absorbent and linear expansivity, have the good thermotolerance and the polyimide resin of processing characteristics simultaneously.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, main purpose of the present invention is to provide a kind of polyimide resin that dissolves in organic solvent.
The polyimide resin that provides a kind of dimensional stability high is provided a further object of the present invention.
Another purpose of the present invention is to provide a kind of polyimide resin of excellent heat resistance.
For reaching above-mentioned and other purpose, the invention provides a kind of by comprising the dianhydride monomer shown in the formula (I) at least
In the formula, R is Sauerstoffatom or O (CH
2)
nO, wherein n is 0 to 2 integer;
And the diamine monomer shown in the formula (II)
H
2N-Ar-NH
2 (II)
In the formula, Ar is that aromatic group is as follows,
Use above-mentioned specific dianhydride monomer and diamine monomer to react, biphenyl structural is imported the main chain part of polyimide resin, improve the structure of polyimide resin, make it dissolve in organic solvent, take into account the thermotolerance and the dimensional stability of polyimide resin simultaneously.
The present invention also provides a kind of method of making polyimide resin, this method makes and comprises the diamine monomer shown in dianhydride monomer shown in the formula (I) and the formula (II) at least, under the condition that solvent exists, carry out polyreaction and form polyamic acid resin, then carry out imidization reaction and form polyimide resin.Polyimide resin of the present invention has solubility, may be dissolved in organic solvent and is modulated to varnish, as the tackiness agent of preparation laminated plates and the usefulness of IC encapsulation.
In sum, compared with prior art, polyimide resin of the present invention dissolves in organic solvent, dimensional stability height, excellent heat resistance.
Embodiment
Below by specific specific examples explanation embodiments of the present invention.
Polyimide resin of the present invention is by comprising the dianhydride monomer shown in the formula (I) at least
In the formula, R is Sauerstoffatom or O (CH
2)
nO, n are 0 to 2 integer, and n is preferably 0 or 2 integer;
And the diamine monomer shown in the formula (II)
H
2N-Ar-NH
2 (II)
In the formula, Ar is that aromatic group is as follows,
Polyimide resin of the present invention is to be formed by the dianhydride monomer of formula (I) and other monomer polymerization, introduces ester class functional group by the dianhydride monomer of formula (I) in polyimide resin, can increase the solubleness of polyimide resin of the present invention in organic solvent.Moreover, in polyimide resin, also introduce the biphenyl class functional group of containing liquid crystal structure by the dianhydride monomer of formula (I), the water-intake rate of polyimide can be reduced, and the thermal expansivity of polyimide resin can be adjusted.The solubleness that increases polyimide resin can increase its applicability, reduces processing stability and dimensional stability that water-intake rate then can improve polyimide resin.Metal levels such as the thermal expansivity of polyimide resin and Copper Foil are close more, and it is can be in high temperature process not Texturized and reduce dimensional stability then to make wiring board.
Embodiments of the invention use dianhydride monomer except comprising the dianhydride monomer shown in the formula (I), also can contain other dianhydride monomer, the example comprises, but non-ly is limited to 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 4, four kinds of dianhydride monomers of 4 '-oxygen, two benzene dianhydrides (ODPA).In the example example, the R of the dianhydride shown in the formula (I) can be Sauerstoffatom or O (CH
2)
nO, when R was Sauerstoffatom, the dianhydride of formula (I) was called PBTDA; When n is 2, then R is OCH
2CH
2During O, the dianhydride of formula (I) is called BHEBPDA.
The preparation of PBTDA can be obtained by existing method, and for example the special public clear 43-5911 of Japanese Patent is a solvent with benzene and toluene, with anhydrous chloride and glycols prepared in reaction; And for example the special public clear 43-189145 of Japanese Patent does transesterify and obtains product with anhydrous acidulants trimellitic acid 1,2-anhydride (TMA, Trimelltic Anhydride) and diester class in the two benzene kind solvents of hydrogenation.The PBTDA method for making is shown in reaction formula 1.
Reaction formula 1
The preparation of BHEBPDA can be obtained by existing method, for example uses BHEBP and TMA to carry out transesterification reaction and obtains, and this method such as the special routine JP10-330306 of Japan disclose.Its synthetic method of BHEBPDA such as reaction formula 2.
Reaction formula 2
Wherein, in the total amount of dianhydride monomer, the content of the dianhydride monomer shown in the formula (I) is preferable with 5 to 20 moles of %; This 3,3 ', 4, the monomeric content of 4 '-benzophenone tetracarboxylic dianhydride (BTDA) is preferable with 60 to 80 moles of %; This 3,3 ', 4, the content of 4 '-biphenyl tetracarboxylic dianhydride monomer (BPDA) is preferable with 10 to 20 moles of %; 4, the content of 4 '-oxygen hexichol dianhydride monomer (ODPA) is preferable with 5 to 15 moles of %.
Polyimide resin of the present invention is except the diamine monomer of formula (II), also can comprise one or more other diamine monomers, the example comprises, but non-ly be limited to 2,2 '-two-[4-(4-amido phenoxy group) phenyl] propane (BAPPP), 4,4 '-two-(4-amido phenoxy group) biphenyl (BAPB), two [4-(4-amido phenoxy group) phenyl] sulfone (BAPS), 3, two phenylsulfone (the DDS of 3 '-diamine base, 3,3 '-Diaminodiphenylsulfone) and 1, two (the 4-amido phenoxy group) benzene (APB, 1,4-Bis (4-aminoPhenoxy) benzene) of 4-.
In the polyimide resin of the present invention, the ratio of dianhydride monomer and diamine monomer in mole number, is preferably between 0.75 to 1.25, and better is between 0.9 to 1.1.Polyimide resin of the present invention is to make diamines and dianhydride monomer be dissolved in non-protonic solvent respectively earlier, carries out polyreaction and forms polyamic acid resin.The example of this non-protonic solvent comprises, but non-N-N-methyl-2-2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF) and composition thereof of being limited to.When forming polyamic acid resin, can dianhydride be added in batches react again earlier with above-mentioned dissolution with solvents diamines.Also can add organic solvent in the above-mentioned non-protonic solvent, the example of this organic solvent comprises, but non-benzene, toluene, hexalin and composition thereof of being limited to.The consumption of this organic solvent is not allow polyamic acid resin be precipitated as principle.
The range of reaction temperature of this dianhydride and diamines is preferably 0 to 100 ℃, is more preferred from 0 to 80 ℃ again.The preferably, this polyamic acid resin solution comprises that solid type composition accounts for solution proportion 5 to 50%; Better person is Gu the type composition accounts for solution proportion 10 to 30%.
When making polyimide resin, be above-mentioned polyamic acid resin adding triethylamine and acetic anhydride etc. to be carried out chemical cyclization at low temperatures become polyimide resin, or adding is as the entrainer of toluene or dimethylbenzene, elevated temperature carries out the reflux dewatering cyclisation and becomes polyimide resin again, then adds methyl alcohol and is precipitated as powder by reaction product.
When polyimide resin of the present invention was used to make flexible circuit board, the thickness of this polyimide resin layer was generally 5 to 100 microns.This metal level can be Copper Foil, aluminium foil, nickel foil or iron foil; Wherein, Copper Foil can be electrolytic copper foil or rolled copper foil, and its thickness is generally 12 to 70 microns.Production method can be coated polyamic acid resin the alligatoring face of above-mentioned metal level earlier, and coating method can use punch die coating machine (diecoater), lip formula coating machine (lipcoater) or cylinder coating machine (rollcoater) coating.Coating is finished and is placed on baking oven and removes solvent with type of heating stage by stage, and making solvent is below 20%.Storing temperature is generally 110 to 180 ℃, is preferably 120 to 170 ℃.Baking speed is generally 0.5 to 10m/min, is preferably 1 to 7m/min.
Then, perhaps add tertiary amine class or acetic anhydride, make the polyamic acid resin imidization become polyimide resin in the lesser temps slaking with high-temperature maturing (curing).Slaking can take a continuous mode or a batch mode mode to place baking oven for heating to realize.The back segment curing temperature is 200 to 400 ℃, is preferably 250 to 350 ℃.The chemical curing temperature that adds tertiary amine class or acetic anhydride is 200 to 300 ℃.Can use nitrogen or non-active gas environment in baking oven, the protection metal level can oxidation in the baking oven for heating process.
Polyimide resin powder dissolution of the present invention can be allocated as varnish (varnish) at non-proton property polar organic solvents such as NMP, DMAC or DMF, it is coated on the polyimide base material (as commercially available prod such as Kapton, Apical or Upilex), uses as solid.The polyimide base material of coating varnish is removed solvent in baking oven baking, again with as metal laminates such as Copper Foil synthesize flexible circuit board as the double-layer wiring plate.Polyimide resin thermotolerance of the present invention is good, then intensity height, can improve as epoxy is that resin solid or acryl are that existing solid such as resin solid has the bad shortcoming of thermotolerance, avoid the resin solid at high temperature deterioration cause the wiring board quality to reduce.
Polyimide resin of the present invention also can be used for the encapsulation of electronic mechanism or electronic component, for example can be used for the protective membrane that covers of unicircuit (IC) element or photodiode (LED) assembly.Polyimide resin of the present invention also can with contain the polyimide resin that the sensitization based compound is mixed into sensing optical activity and be applied in unicircuit (IC) manufacturing.In addition, polyimide resin of the present invention can be made into film (film) or is modulated into varnish (varnish), is used to make the high mulch film of thermotolerance, for example is used for the mulch film of soft board.Polyimide resin of the present invention also can with the high-k material as barium titanate, make film after the blending, as internal embedded electronic component as electric capacity.
The raw material explanation
BTDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
BPDA:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride
ODPA:4,4 '-oxygen, two benzene dianhydrides
TPE-R:1, two (the 4-amido phenoxy group) benzene of 3-
BAPP:2,2 '-two-[4-(4-amido phenoxy group) phenyl] propane
BAPS: two [4-(4-amido phenoxy group) phenyl] sulfone
APB:1, two (the 4-amido phenoxy group) benzene of 4-
BAPB:4,4 '-two-(4-amido phenoxy group) biphenyl
The NMP:N-N-methyl-2-2-pyrrolidone N-
DMAC: N,N-DIMETHYLACETAMIDE
DMF: dimethyl formamide
The physical property measurement method
(1) water-absorbent: according to IPCTM-6502.6.2
The heat-resisting test in (2) half fields: according to IPCTM-6502.4.13
(3) stripping strength (Peel Strength): according to IPCTM-6502.4.9
(4) Tg: record temperature glass tansition temperature (Tg) with thermomechanical analysis
Embodiment 1
Insert the APP (0.06 mole) of 24.6 grams and the NMP of 160 grams and dissolve in four neck reactors with stirrer and nitrogen conduit, nitrogen flow is 20cc/min, stirs after the dissolving, keeps 15 ℃.
Getting four flasks that have stirrer respectively inserts first flask with the NMP of the BPDA (0.01 mole) of 2.94 grams and 10 grams and stirs and make its dissolving.The PBTDA (0.0025 mole) of 1.34 grams and the NMP of 10 grams are inserted second flask, stir and make its dissolving.The solution of first and second flask is added in the reactor, continue to import nitrogen, stir and reacted 1 hour.
The ODPA (0.01 mole) of 3.1 grams and the NMP of 10 grams are inserted the 3rd flask, stir and make its dissolving.The solution of flask is added in the reactor, continue to import nitrogen, stir and reacted 1 hour.
With the BTDA (0.0375 mole) of 12.08 grams and NMP the 4th flask of 50 grams, stir and make its dissolving.Then, add in the reactor, continue to import nitrogen, under 15 ℃ condition, reacted 4 hours, generate polyamic acid resin every four solution of 30 minutes branches with the 4th flask.
Stop to import nitrogen, reactor is loaded onto Dean stack dewater.The toluene of getting 35 grams adds in the reactor, temperature is risen to 185 ℃ carry out the endless loop dehydration reaction, makes polyamic acid resin form polyimide resin.Utilize refluxing toluene to continue water is taken out of, after confirming anhydrous being taken out of, cool the temperature to room temperature.Then add methyl alcohol and make the pi resin precipitated, filtering precipitate utilizes washed with methanol throw out twice, dries in baking oven, obtains the pi toner.
The polyimide resin of getting 0.5 gram is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 15 grams, uses viscometer to be 1.16dl/g in 25 ℃ of intrinsic viscosity (IV).
Embodiment 2 to embodiment 10
Repeat the step of embodiment 10, the mole number consumption of each composition is as shown in table 1.
Comparative example 1 and comparative example 2
Repeat the step of embodiment 1, the mole number consumption of each composition is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | |
| BPDA | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.040 |
| BTDA | 0.075 | 0.07 | 0.065 | 0.060 | 0.075 | 0.07 | 0.07 | 0.07 | 0.07 | 0.07 | 0.08 | 0.050 |
| ODPA | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| PBTDA | 0.005 | 0.01 | 0.015 | 0.02 | 0.01 | 0.01 | 0.01 | 0.01 | ||||
| BHEB PDA | 0.005 | 0.01 | ||||||||||
| BAPP | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |||||
| BAPB | 0.1 | |||||||||||
| BAPS | 0.1 | |||||||||||
| BAPS-M | 0.1 | |||||||||||
| TPE-R | 0.1 | |||||||||||
| APB | 0.1 | |||||||||||
| Limiting viscosity (dl/g) | 1.16 | 0.97 | 1.25 | 1.31 | 0.92 | 0.85 | 0.93 | 1.22 | 0.95 | 0.83 | 0.92 | 1.13 |
The pi toner of the foregoing description 1 to embodiment 10 and comparative example 1 and comparative example 2 gained is dissolved in solvent, the results are shown in table 2.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | |
| NMP | + | + | + | + | + | + | + | + | + | + | + | * |
| DMAC | + | + | + | + | + | + | + | + | + | + | * | * |
| DMF | + | + | + | + | + | + | + | + | + | + | - | - |
"+" expression dissolving; "-" expression is insoluble; Dissolving after " * " expression heats up
The pi toner of the foregoing description 1 to embodiment 10 and comparative example 1 and comparative example 2 gained is dissolved in NMP, be deployed into the varnish (varnish) of solid type part 15%, be coated on thickness and be on 25 microns the polyimide film (trade(brand)name Apical), 6 microns of coating thicknesss.Use baking oven in 150 ℃ of heating 5 minutes, and carry out drying under 15 minutes the condition of 180 ℃ of heating and remove solvent.Finish the inferior film of polyamides and the blank Copper Foil that will scribble polyimide resin after the drying and utilize high temperature pressing machine 280 ℃ to 400 ℃ pressings, preferable temperature is 300 to 360 ℃, and pressing pressure is 20 to 200kg/cm
2, preferable pressure is 40～150kg/cm
2Obtain the two-sided Copper Foil wiring board of polyimide resin, utilize IPCTM-650 test Copper Foil stripping strength, the results are shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | |
| Tg(℃) | 234 | 243 | 247 | 235 | 234 | 226 | 235 | 225 | 228 | 238 | 236 | 247 |
| Stripping strength (kgf/cm) | 1.1 | 1.1 | 1.3 | 1.2 | 1.4 | 1.3 | 1.2 | 1.4 | 1.7 | 1.4 | 0.8 | 0.7 |
| Heat-resisting test (288 ℃ of 10sec) | By | By | By | By | By | By | By | By | By | By | By | By |
As shown in Table 3, the two-sided Copper Foil wiring board made by polyimide resin of the present invention has preferable stripping strength (greater than 1.0kg/cm), and hence one can see that, and the made flexible circuit board of polyimide resin of the present invention has existing person's excellent specific property.
Claims (29)
1. the polyimide resin with solubility is characterized in that, this resin is by comprising the dianhydride monomer shown in the formula (I) at least
Wherein, R be Sauerstoffatom or-O (CH
2)
nO-, n are 0 to 2 integer;
And the diamine monomer shown in the formula (II)
H
2N-Ar-NH
2 (II)
In the formula, Ar is expression
Carry out polyreaction and form polyamic acid resin, then carry out imidization and form.
2. polyimide resin as claimed in claim 1 is characterized in that, n is 0 or 2 integer.
3. polyimide resin as claimed in claim 1 is characterized in that, the ratio of this dianhydride monomer and diamine monomer is between 0.75 to 1.25 in mole number.
4. polyimide resin as claimed in claim 2 is characterized in that, the ratio of this dianhydride monomer and diamine monomer is between 0.9 to 1.1 in mole number.
5. polyimide resin as claimed in claim 1 is characterized in that this dianhydride monomer also comprises 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride monomer and 4,4 '-oxygen, two benzene dianhydrides.
6. polyimide resin as claimed in claim 5 is characterized in that, the content of the dianhydride monomer shown in the formula (I) is 5 to 20 moles of % in the total amount of dianhydride monomer.
7. polyimide resin as claimed in claim 5 is characterized in that, 3,3 ', 4, and the monomeric content of 4 '-benzophenone tetracarboxylic dianhydride is 60 to 80 moles of % in the total amount of dianhydride monomer.
8. polyimide resin as claimed in claim 5 is characterized in that, 3,3 ', 4, and the monomeric content of 4 '-biphenyl tetracarboxylic dianhydride is 10 to 20 moles of % in the total amount of dianhydride monomer.
9. polyimide resin as claimed in claim 5 is characterized in that, 4, and the content of 4 '-oxygen hexichol dianhydride monomer is 5 to 15 moles of % in the total amount of dianhydride monomer.
10. a resinous varnish is characterized in that, this resinous varnish comprises polyimide resin as claimed in claim 1 and solvent, and varnish makes through reconciling into.
11. resin tackiness agent as claimed in claim 10 is characterized in that, this varnish is the resin tackiness agent.
12. resin tackiness agent as claimed in claim 10 is characterized in that, this solvent is to be selected from N-N-methyl-2-2-pyrrolidone N-, N,N-DIMETHYLACETAMIDE or dimethyl formamide to constitute a kind of in the group.
13. resin tackiness agent as claimed in claim 10 is characterized in that, the solid of this polyimide resin in this varnish is 5 to 50%.
14. resin tackiness agent as claimed in claim 10 is characterized in that, the solid of this polyimide resin in this varnish is 10 to 30%.
15. a method of using resinous varnish as claimed in claim 10 to prepare flexible circuit board is characterized in that this method comprises the following steps:
Polyimide resin varnish is coated on the tinsel; And
Add the heat abstraction solvent.
16. method as claimed in claim 15 is characterized in that, this method also comprises the following steps:
Do not fit the one side of tinsel with pressuring method another tinsel of fitting at polyimide resin varnish; And
Heat hardening resin combination under nitrogen is made the double-surface flexible circuit card of tinsel-resin-metal paper tinsel.
17., it is characterized in that this tinsel is that Copper Foil, aluminium foil, nickel foil or Alloy Foil constitute a kind of in the group as claim 15 or 16 described methods.
18. a method of making polyimide resin is characterized in that this method comprises the following steps:
(a) use dissolution with solvents to comprise the dianhydride monomer shown in the formula (I) at least respectively
In the formula, R be Sauerstoffatom or-O (CH
2)
nO-, n are 0 to 2 integer;
And the diamine monomer shown in the formula (II)
H
2N-Ar-NH
2 (II)
In the formula, Ar is the expression diamine monomer, and it comprises
(b) will add in the dissolved diamine monomer through the dissolved dianhydride monomer in batches, carry out polyreaction and form polyamic acid resin; And
Carry out imidization and form polyimide resin.
19. method as claimed in claim 18 is characterized in that, n is 0 to 2 integer.
20. method as claimed in claim 18 is characterized in that, the ratio of this dianhydride monomer and diamine monomer is between 0.75 to 1.25 in mole number.
21. method as claimed in claim 20 is characterized in that, the ratio of this dianhydride monomer and diamine monomer is between 0.9 to 1.1 in mole number.
22. method as claimed in claim 18 is characterized in that, this dianhydride monomer also comprises 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride monomer and 4,4 '-oxygen, two benzene dianhydrides.
23. method as claimed in claim 22 is characterized in that, the content of the dianhydride monomer shown in the formula (I) is 5 to 20 moles of % in the total amount of dianhydride monomer.
24. method as claimed in claim 22 is characterized in that, 3,3 ', 4, and the monomeric content of 4 '-benzophenone tetracarboxylic dianhydride is 60 to 80 moles of % in the total amount of dianhydride monomer.
25. method as claimed in claim 22 is characterized in that, 3,3 ', 4, and the monomeric content of 4 '-biphenyl tetracarboxylic dianhydride is 10 to 20 moles of % in the total amount of dianhydride monomer.
26. method as claimed in claim 22 is characterized in that, 4, and the content of 4 '-oxygen hexichol dianhydride monomer is 5 to 15 moles of % in the total amount of dianhydride monomer.
27. method as claimed in claim 18 is characterized in that, this solvent is to constitute a kind of in the group by N-N-methyl-2-2-pyrrolidone N-, N,N-DIMETHYLACETAMIDE or dimethyl formamide.
28. method as claimed in claim 18 is characterized in that, also comprises the step of adding organic solvent in this step (b), this organic solvent is the group that is made of benzene, toluene, hexane and hexalin.
29. method as claimed in claim 18 is characterized in that, the temperature of this step (b) is 0 to 100 ℃, is good with 10 to 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100748742A CN100523051C (en) | 2005-06-03 | 2005-06-03 | Dissoluble polyimide resin, and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100748742A CN100523051C (en) | 2005-06-03 | 2005-06-03 | Dissoluble polyimide resin, and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1872895A true CN1872895A (en) | 2006-12-06 |
| CN100523051C CN100523051C (en) | 2009-08-05 |
Family
ID=37483510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100748742A Expired - Fee Related CN100523051C (en) | 2005-06-03 | 2005-06-03 | Dissoluble polyimide resin, and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100523051C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573842A (en) * | 2016-07-04 | 2018-01-12 | 大亚电线电缆股份有限公司 | The polyimide insulative coating and enamel-covered wire of low dielectric |
| CN109679095A (en) * | 2018-12-18 | 2019-04-26 | 苏州予信天材新材料应用技术有限公司 | A kind of high temperature resistant type polyamide-polyether acid imide toughening polymer and preparation method thereof |
| CN109679096A (en) * | 2018-12-20 | 2019-04-26 | 中国石油大学(华东) | A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field |
-
2005
- 2005-06-03 CN CNB2005100748742A patent/CN100523051C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573842A (en) * | 2016-07-04 | 2018-01-12 | 大亚电线电缆股份有限公司 | The polyimide insulative coating and enamel-covered wire of low dielectric |
| CN107573842B (en) * | 2016-07-04 | 2020-05-12 | 大亚电线电缆股份有限公司 | Low-dielectric polyimide insulating paint and enameled wire |
| CN109679095A (en) * | 2018-12-18 | 2019-04-26 | 苏州予信天材新材料应用技术有限公司 | A kind of high temperature resistant type polyamide-polyether acid imide toughening polymer and preparation method thereof |
| CN114621440A (en) * | 2018-12-18 | 2022-06-14 | 苏州予信天材新材料应用技术有限公司 | High-temperature-resistant polyamide-polyetherimide toughened polymer and preparation method thereof |
| CN109679096A (en) * | 2018-12-20 | 2019-04-26 | 中国石油大学(华东) | A kind of novel hot imidization method prepares the application of PI and Ultra filtration membrane field |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100523051C (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106010421B (en) | Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper-clad laminate, wiring board, and printed wiring board | |
| CN1238401C (en) | Polyimide copolymer and methods for preparing same | |
| EP1300444A1 (en) | Epoxy resin composition and cured object obtained therefrom | |
| CN1406262A (en) | Adhesive polyimide resin and adhesive laminate | |
| CN113474380A (en) | Polyamic acid resin, polyimide resin, and resin composition containing same | |
| KR100733105B1 (en) | Polyimide Film, Method of Manufacture, and Metal Interconnect Board with Polyimide Film Substrate | |
| CN101068851A (en) | Polyimide, polyimide film and laminated body | |
| CN1898298A (en) | Aromatic polyamic acid and polyimide | |
| CN101787126A (en) | Polyamide acid composition, method for manufacturing two-layer process flexible copper-clad plates by use of same, and obtained two-layer process flexible copper-clad plate | |
| JP4478095B2 (en) | Polyamideimide resin modified with polyoxyalkyleneamine and composition thereof | |
| CN1063134C (en) | Medlin-metal-foil composite film | |
| CN100523051C (en) | Dissoluble polyimide resin, and preparation method | |
| CN100339416C (en) | Polyimide resin for electrical insulating material | |
| JPH11199668A (en) | Polytmide composition, and tape for tab and flexible printed circuit board therefrom | |
| CN1872896A (en) | New type polyimide resin, and preparation method | |
| JP5270865B2 (en) | Adhesive and its use | |
| JP4527687B2 (en) | Soluble polyimide resin and method for producing the same | |
| KR20020016552A (en) | Polyimide Film, Method of Manufacture, and Metal Interconnect Board with Polyimide Film Substrate | |
| JP5505240B2 (en) | Polyamideimide resin and method for producing the same | |
| JP5000074B2 (en) | Method for producing polyamideimide | |
| JP2005314630A (en) | Aromatic polyamic acid and polyimide | |
| TWI789796B (en) | Polymer and application thereof | |
| JP4761108B2 (en) | Method for producing silane-modified polyamic acid fine particles, method for producing polyimide-silica composite fine particles, composite fine particles and conductive fine particles | |
| JP2005325147A (en) | Method for producing polyamic acid-silica composite fine particle, method for producing polyimide-silica composite fine particle, composite fine particle and electroconductive fine particle | |
| CN1856558A (en) | Adhesive aid composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20150603 |
|
| EXPY | Termination of patent right or utility model |