CN105601922A - Polyamide acid for producing flexible copper plate coated with no rubber through two-layer method and preparing method of polyamide acid - Google Patents
Polyamide acid for producing flexible copper plate coated with no rubber through two-layer method and preparing method of polyamide acid Download PDFInfo
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- CN105601922A CN105601922A CN201610059618.4A CN201610059618A CN105601922A CN 105601922 A CN105601922 A CN 105601922A CN 201610059618 A CN201610059618 A CN 201610059618A CN 105601922 A CN105601922 A CN 105601922A
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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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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Abstract
Polyamide acid for producing a flexible copper plate coated with no rubber through a two-layer method is prepared by polymerizing three kinds of monomer aromatic diamine at the ratio of (2-6):(2-6):1, wherein the three kinds of monomer aromatic diamine are 3,4'-diaminodiphenyl ether, p-phenylenediamine and 2-(4-amino-phenyl)-5-minobenzimidazole with the CAS register number of 7621-86-5, and the molecular structure of 2-(4-amino-phenyl)-5-minobenzimidazole is shown in the specification. The three kinds of substances are dissolved in an N,N-dimethyl formamide solvent, the mixture is cooled to minus 10-minus 5 DEG C to be reacted for 40-50 h, and thus a polyamide acid solution is generated through polymerization, wherein according to the polyamide acid solution, the solid content ranges from 10 g/100 ml to 15 g/100 ml, the viscosity is larger than or equal to 8000 cp, the number-average molecular weight ranges from 50000 to 76000, and the molecular weight distribution index is smaller than 1.4. The molecular structure of polyamide acid synthesized in the way is matched with the copper expansion coefficient CTE; the specific functional group diamine with an imidazole structure is introduced so that amine on imidazole can form a coordination key with copper, connection with copper can be enhanced, and thus the adhesive force between a finished polyamide acid membrane and copper foil is increased.
Description
Technical field
The present invention relates to flexible printed wiring board field, relate in particular to by two-layer legal system for flexible glue-free coated polyimideIn copper coin process, its polyimide precursor---polyamic acid and preparation method thereof.
Background technology
Polyimide copper clad lamination, with its unique property of interconnections, obtains and extensively should in fields such as telecommunication, computer, automobilesWith, the whole world is with 10%～15% annual growth sustainable growth, and within 2013, global consumption exceedes 1,500,000,000 dollars. There is at present glue polyamidesImines copper-clad plate is due to its flexility, heat resistance, and dimensional stability is not good, and application is very limited. And glue-free polyamidesImines copper-clad plate and tradition have the comparison of glue polyimide copper clad lamination, and heat resistance is greatly improved, and the region life-span of destroying or force to yield is significantly carriedHeight, Rigid Flex has been realized high density interconnect, has greatly improved the link efficiency of circuit.
At present, nearly all adopting two-layer method to produce glue-free is abroad polyimide copper clad lamination, in two-layer method according to differenceTechnique is divided into again 4 kinds of manufacture methods, that is: the tape casting, and metallikon, chemical plating/galvanoplastic and laminating, but said method all needsExpensive special import equipment, cost is high, complex process, and speed is at 2-3m/min, and efficiency is low, energy consumption is high. And glue-free system is poly-The dimensional stability of acid imide copper-clad plate is a huge test. Polyimides will combine with copper, due to the two(CET) is different for thermal coefficient of expansion, is being subject to cold and hot effect, especially by warm at high the precursor polyamic acid of polyimidesWhen cooling after imidizate, will there is warpage because of not mating of both thermal coefficient of expansions, the even delamination of ftractureing, cause existingThere is the poor dimensional stability of glue-free copper coated plate. Polyamic acid is the precursor of polyimides, and its chemical constitution has directly determined polyamidesThe performance of imines, in prior art, the molecular structure of synthesizing polyamides acid is difficult to mate very much with copper coefficient of expansion CTE, causes intoAdhesive force between product polyimide film and Copper Foil is not ideal enough, dimensional stability is good not.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of molecular structure and mates very much, is beneficial to copper coefficient of expansion CTEPolyamic acid of the glue-free high-dimensional stability that is polyimide copper clad lamination composite and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides in order to solve the problems of the technologies described above, the invention provides useThe polyamic acid of producing flexible glue-free copper coated plate in two-layer method, is characterized in that: be to be polymerized by 3 kinds of monomer aromatic diamines, and 3Planting monomer aromatic diamines is: 3,4-diaminodiphenyl ether, p-phenylenediamine (PPD) and molecular structure areCASAccession number is 2-(4-aminophenyl)-5-aminobenzimidazole of 7621-86-5, and its proportioning is 2-6:2-6:1.
Meanwhile, the present invention also provides the preparation method of above-mentioned polyamic acid, it is characterized in that: in reactor, will joinThan 3 kinds of monomer aromatic diamines for 2-6:2-6:1---
3,4-diaminodiphenyl ether, p-phenylenediamine (PPD) and molecular structure areCAS loginNumber be 2-(4-aminophenyl)-5-aminobenzimidazole of 7621-86-5---be dissolved in DMF solvent, coldBut to-10 degrees Celsius to-5 degrees Celsius, in 5-10 hour, divide 5-10 batch add total amount and monomer aromatic diamines equimolarAromatic tetrahydric dianhydride, then maintains-10 degrees Celsius to-5 degrees Celsius, and reaction 40-50 hour makes its polymerization generation solid content be10-15 gram/100 milliliters and viscosity are more than or equal to that 8000cp, number-average molecular weight are 50000～76000, molecular weight distributing index <1.4 polyamic acid solution; React as follows:
Preferred solvent used is that water content is lower than 100ppm through the DMF of molecular sieve dehydration processing.
Described aromatic tetrahydric dianhydride is preferably pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3, and 3 ', 4,4 '---hexicholOne in ketone tetracarboxylic dianhydride and 4-4 Biphenyl Ether dianhydride.
Beneficial effect of the present invention is mainly described below:
For glue-free be for the dimensional stability of polyimide copper clad lamination, the main way of solution makes to interosculateThe thermal coefficient of expansion of bi-material approaches as far as possible, and affect material thermal expansion coefficient (CTE) because have chemical constitution and gatheringTwo aspects of state, after chemical constitution is determined, state of aggregation determined by more factor, for example solvent for use, synthesizedJourney, coating method, drying program, imidizate program, annealing conditions etc.
For synthesizing of polyamic acid, polyamic acid is the precursor of polyimides, and its chemical constitution has directly determined polyamidesThe performance of imines, by MOLECULE DESIGN and repeatedly experiment revise, the molecular structure of the synthetic polyamic acid of the present invention and copper expansionCoefficient CTE coupling, by introducing characteristic functional group---containing the diamines of glyoxaline structure, the amine on imidazoles can form coordination with copperStrong, enhancing is connected with copper, thereby has improved the adhesive force between finished product polyimide film and Copper Foil.
In synthetic process, owing to reaction being controlled to the low-temperature condition of-10 degrees Celsius to-5 degrees Celsius, can obtainThe polymer of HMW, meanwhile, owing to adding aromatic tetrahydric dianhydride to be under long period interval, to add gradually for point multiple times, make molecular weight distributing index lower than 1.4, these are for the precursor that obtains the polyimides mating with Copper Foil CTE---and poly-Amic acid is very important.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
Fig. 1 is the production line schematic diagram of the two-layer legal system of the present invention for flexible glue-free polyimide copper clad lamination.
Fig. 2 is nitrogen high temperature oven schematic diagram of the present invention.
Fig. 3 is A portion enlarged drawing in Fig. 2.
Detailed description of the invention
Embodiment 1
As shown in Figure 1, two-layer legal system of the present invention, for the production line of flexible glue-free polyimide copper clad lamination, comprises system successivelyThe reaction system 100 of standby polyamic acid solution, by polyamic acid solution be applied to the coating system 200 of Copper Foil, by after coatingThe high-tension drying cylinder 300 of copper-clad plate redrying under high-tension, web-like product is carried out to the special nitrogen high temperature of imidizateBaking oven 400.
Described reaction system 100, the coating system 200 of preparing polyamic acid solution can adopt equipment of the prior art,Wherein coating system 200 can adopt the equipment in existing coating field; And the parameter of high-tension drying cylinder 300 and special nitrogen high temperature dry400, case is special designs of the present invention.
Described high-tension drying cylinder 300 is undertaken on coating system 200 ends, the drying cylinder structure that can adopt paper industry to use,The copper conduction oil cylinder body that for example can rotate around its axle center, but the present invention finds the Parameter Conditions to described drying cylinder through great many of experimentsMust particular/special requirement, such as drying cylinder diameter, surface state, surface temperature difference scope, static balancing value etc. In the present embodiment, dryThe drying section diameter that cylinder contacts with copper-clad plate is 1.5 meters, and cylinder surface is electroplate with the chromium layer that 0.08-0.1mm is thick and does minute surface placeReason, uniform heating element heater in cylinder body, its cylinder surface temperature difference, in 3 degree, is undertaken on cylinder surface copper-clad plate high-tension and entersRow heat drying. The static balancing of cylinder body requires, below 40g, to make tension force more even.
As shown in Figure 2, described nitrogen high temperature oven 400 comprises body of heater 10, the salable heat insulation furnace cover 20 in body of heater, is bakingVacuum system 40 that case vacuumizes, gas charging system for baking oven inflated with nitrogen, circulating fan system 60, for baking oven power supply, heating and cooling,The control system of gas control; Also comprise the bin 70 that is placed in body of heater inner bottom part; Described body of heater 10 is vertical hollow circle tube, instituteState body of heater 10 and comprise successively from outside to inside furnace shell 11, heat-insulation layer 12, outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15, described inOuter thermal insulation layer 13, heating element heater 14, inner insulating layer 15 form flue, and the heating element heater 14 of described body of heater is heating wire, for stoveTemperature is more even in courage, around furnace body inside wall, on inner insulating layer 15, be provided with multiple through holes 151 of conducting heat be convenient to. InstituteState and in flue, be provided with the bin 16 that is supported in bottom of furnace body; Connect a hydraulicefficiency elevation structure 30 at described body of heater lateral wall, bagDraw together the hydraulic cylinder 31 that is connected to described body of heater side, the piston 32 of hydraulic cylinder is connected in the lower end of longitudinal extension bar 33, and longitudinallyThe top, upper end of expansion link 33 is fixedly connected on described lifting arm 33, thus by hydraulic piston 32 drive lifting arm rise or underFall, so as by described heat insulation furnace cover 20 lock sealings in body of heater top open part or open it. Described vacuum system 40 comprisesBe placed in the vavuum pump 41 of body of heater outside, vacuum line 42 one end are communicated in vavuum pump, and the other end is communicated in described flue, connectorBe provided with valve 43; (complete illustrating not in figure, with reference to the nitrogen inflation system of association area in prior art for described nitrogen gas charging systemSystem), comprise the air inlet 51, air valve, the pipeline that are opened in flue and can be communicated with body of heater external air source; Described circulating fan isSystem 60 is by motor 61 and be connected in the fan blade 62 of motor output end, and described air intake leaf is two, is symmetricly set on bottom of furnace bodyBoth sides; Described bin 70 comprises that connection is supported in the underframe 71 of bottom of furnace body, and is connected to the framework 72 on underframe top, canAccept multiple polyimide copper clad lamination material volumes 80. For sealing better, be provided with in downside and the body of heater contact position of described bellOne circle groove, is equipped with fluid sealant 21 in groove, in the periphery of fluid sealant, in being respectively equipped with on bell and body of heater as cold fluid sealantBut the many water cooling tubes 22 of effect, are unlikely to allow fluid sealant keep lower temperature to damage.
On this production line, as follows for the step of glue-free polyimide copper clad lamination by two-layer legal system:
1) in reactor, by monomer aromatic diamines 3,4-diaminodiphenyl ether, p-phenylenediamine (PPD) and 2-(4-aminophenyl)-3 kinds of materials of 5-aminobenzimidazole are according to 2:2:1 mol ratio, be dissolved in through molecular sieve dehydration processing, water content is lower than 100ppmDMF solvent in, be cooled to-10 about degree, in 5 hours, points 5 batches add with diamines material total amount etc.Mole pyromellitic acid anhydride, maintain-10 degree left and right, react 40 hours, and polymerization generation solid content is 15 grams/100 millilitersPolyamic acid solution, the number-average molecular weight of the polyamic acid obtaining is 51000～66000, molecular weight distributing index is < 1.4, forThe polyamic acid solution of HMW, low profile exponent.
2) be 0.2% thermal instability defoamer to adding weight percentage in polyimide solution, stir,Described thermal instability defoamer refers to resolvent defoamer in heating process, makes the glue-free polyamides Asia in the end obtainingIn amine copper-clad plate, do not have residual. Thermal instability defoamer of the present invention adopts the TEGOAirex920 photocuring of Di Gao companyCoating dedicated defoamer, also can adopt TEGOFlow370 solvent-borne type levelling agent, the TEGOFlow300 of Di Gao company moltenFormulation levelling agent or TEGOAirex940 solvent-borne type, no-solvent type coating defoamer.
3) by step 2) polyamic acid solution that obtains coats on the Copper Foil of 18 micron thick with the speed of 6m/min. CoatingCan adopt coating apparatus general in prior art, in the process of coating, be dried to while removing 89% solvent with 140 degrees Celsius,Then proceed as follows,
3) dry in 180 degrees Celsius, the speed of 4m/min on special drying line, remove residual solvent completely, be wound intoThe web-like of 1000m/ volume.
4) web-like product is put into special nitrogen high temperature oven, heats up: with the speed of 30 degrees Celsius/hour with following processRise to 180 degrees Celsius, then constant temperature 4 hours, rises to 330 degrees Celsius for 2 hours; Then constant temperature carries out imidizate for 1 hour; ThenCarry out temperature-fall period: be down to 270 degrees Celsius by 330 degrees Celsius with the time of 1 hour, constant temperature 2 hours, is cooled to 200 in 2 hours and takes the photographFamily name's degree, then naturally coolingly obtain the copper-clad plate of two-layer method non-gel flexible, the results are shown in Table shown in two of various Performance Detection. Separately,The data such as experiment parameter are with reference to table one.
Embodiment 2
The content of embodiment 2 and embodiment 1 are roughly the same. Difference is:
Step 1) in aromatic amine solution be 3 kinds of materials in embodiment 1, proportioning is 4:4:1, being cooled to temperature is-8 degrees CelsiusLeft and right, in 8 hours, points 8 batches mole bibenzene tetracarboxylic dianhydride such as add, and maintaining-8 degrees Celsius of left and right reaction time is 45Hour, the polyamic acid obtaining admittedly containing be 12 grams/100 milliliters, molecular weight be 53000-69000, molecular weight distributing index is littleIn 1.4.
Step 2) in copper thickness be 12mm, coating speed is 9m/min, when coating, baking temperature is 130 degree, removes81% solvent, step 4) in drying cylinder diameter be 2 meters, be that 190 degrees Celsius, speed are in the dry temperature of high-tension dryer surface3m/min, rolling is 1500m/ volume; When imidizate according to the heating and cooling process of embodiment 1, the constant temperature temperature of 1 hour in the middle of processDegree is 335 degree, the non-gel flexible copper-clad plate obtaining, the results are shown in Table shown in two of various Performance Detection. Separately, the data such as experiment parameterWith reference to table.
Embodiment 3
The content of embodiment 3 and embodiment 1 are roughly the same. Difference is:
Step 1) in aromatic amine solution be 3 kinds of materials in embodiment 1, proportioning is that 6:6:1 chilling temperature is-5 degrees Celsius,In 10 hours, points 10 batches mole 4-4 Biphenyl Ether dianhydride such as add, and maintaining-5 degrees Celsius of reaction time is 50 hours, obtainsPolyamic acid solid containing being that 13 grams/100 milliliters, molecular weight are 51000-64000, molecular weight distributing index is less than 1.4.
Step 2) in copper thickness be 12mm, when coating, baking temperature is 160 degree, speed is 12m/min, removes 80%Solvent; Step 4) in drying cylinder diameter be 2.5 meters, be that 200 degree, speed are 2m/ in the dry temperature of high-tension dryer surfaceMin, rolling is 2000m/ volume; When imidizate according to the heating and cooling process of embodiment 1, the constant temperature temperature of 1 hour in the middle of processBe 340 degree, the non-gel flexible copper-clad plate obtaining, the results are shown in Table shown in two of various Performance Detection. Separately, the data such as experiment parameter ginsengAccording to table.
Embodiment 4
Content in the present embodiment 4 and embodiment 3 are roughly the same. Difference is:
Step 1) while preparing polyamic acid solution, the aromatic diamines of employing is 2 kinds of chemical substances: 3,4-diaminodiphenyl etherWith molecular structure beCAS accession number is 2-(4-the aminophenyl)-5-of 7621-86-5Aminobenzimidazole, its proportioning is 1:1. The aromatic dianhydride that uses is bibenzene tetracarboxylic dianhydride. The polyamic acid obtaining is admittedly containing being13.5 grams/100 milliliters, molecular weight be 50000-65000, molecular weight distributing index is less than 1.4; Coating temperature is 120 CelsiusDegree, speed are 6m/min, remove 80% solvent; In the time of cylinder dried, speed is that 3m/min, temperature are 200 degrees Celsius; After aminationThe non-gel flexible polyimide copper clad lamination obtaining, the results are shown in Table shown in two of various Performance Detection. Separately, the data such as experiment parameter ginsengAccording to table.
Embodiment 5
Content in the present embodiment 5 and embodiment 4 are roughly the same. Difference is:
The aromatic diamines adopting is that 2 kinds of chemical substances are identical with embodiment 4, and its proportioning is adjusted into 1:1.1. The polyamides obtainingAmino acid is admittedly containing being that 12.8 grams/100 milliliters, molecular weight are that 51000-68000, molecular weight distributing index are less than 1.4; At cylinder driedShi Sudu is that 2m/min, temperature are 180 degrees Celsius; The non-gel flexible polyimide copper clad lamination finally obtaining, various Performance DetectionThe results are shown in Table shown in two. Separately, the data such as experiment parameter are with reference to table one.
Embodiment 6
Content in the present embodiment 6 and embodiment 4 are roughly the same. Difference is:
The aromatic diamines adopting is 2 kinds of chemical substances, and identical with embodiment 4, its proportioning is adjusted into 1:1.2. What obtain is poly-Amic acid admittedly containing be 14 grams/100 milliliters, molecular weight be 51000-67000, molecular weight distributing index is less than 1.4; Dry at drying cylinderWhen dry, speed is that 4m/min, temperature are 180 degrees Celsius; The non-gel flexible polyimide copper clad lamination finally obtaining, various performance inspectionsThat surveys the results are shown in Table shown in two. Separately, the data such as experiment parameter are with reference to table one.
Embodiment 7
Content in the present embodiment 7 and embodiment 2 are roughly the same, and difference is that the aromatic diamines of employing is 2 kinds of chemistryMaterial: p-phenylenediamine (PPD) and molecular structure areCAS accession number is the 2-(4-of 7621-86-5Aminophenyl)-5-aminobenzimidazole, its proportioning is 1:1. The tetracarboxylic dianhydride that uses is 3,3 ', 4,4 '---and benzophenone tetracid twoAcid anhydride, the polyamic acid obtaining is admittedly containing being that 11.6 grams/100 milliliters, molecular weight are 52000-69000, molecular weight distributing index is less than1.4; The dry drying cylinder speed of second segment is that 1m/min, temperature are 200 degrees Celsius; The non-gel flexible coated polyimide finally obtainingCopper coin, the results are shown in Table shown in two of various Performance Detection. Separately, the data such as experiment parameter are with reference to table one.
Embodiment 8
Content in the present embodiment 8 and embodiment 7 are roughly the same, and aromatic diamines adopts the same chemical substance of 2 kinds, itsProportioning is adjusted into 1:1.1. The polyamic acid obtaining solid containing being that 11 grams/100 milliliters, molecular weight are 52000-65000, molecular weightProfile exponent is less than 1.4; The non-gel flexible polyimide copper clad lamination finally obtaining, various Performance Detection the results are shown in Table twoShow. Separately, the data such as experiment parameter are with reference to table one.
Embodiment 9
Content in the present embodiment 9 and embodiment 7 are roughly the same, and aromatic diamines adopts the same chemical substance of 2 kinds, itsProportioning is adjusted into 1:1.2. The polyamic acid obtaining solid containing being that 10.8 grams/100 milliliters, molecular weight are 53000-66000, moleculeAmount profile exponent is less than 1.4; The non-gel flexible polyimide copper clad lamination finally obtaining, various Performance Detection the results are shown in Table twoShow. Separately, the data such as experiment parameter are with reference to table one.
Table one
Claims (4)
1. the polyamic acid of producing flexible glue-free copper coated plate for two-layer method, is characterized in that: be poly-by 3 kinds of monomer aromatic diaminesClose and form, 3 kinds of monomer aromatic diamines are: 3,4-diaminodiphenyl ether, p-phenylenediamine (PPD) and molecular structure areCAS accession number is 2-(4-aminophenyl)-5-aminobenzimidazole of 7621-86-5, and its proportioning is 2-6:2-6:1.
2. the preparation method who produces the polyamic acid of flexible glue-free copper coated plate for two-layer method claimed in claim 1, its featureBe: in reactor, 3 kinds of monomer aromatic diamines that are 2-6:2-6:1 by proportioning---
3,4-diaminodiphenyl ether, p-phenylenediamine (PPD) and molecular structure areCAS accession number is2-(4-aminophenyl)-5-aminobenzimidazole of 7621-86-5---be dissolved in DMF solvent, coolingTo-10 degrees Celsius to-5 degrees Celsius, in 5-10 hour, divide 5-10 batch and add total amount and the equimolar virtue of monomer aromatic diaminesFragrant tetracarboxylic dianhydride, then maintains-10 degrees Celsius to-5 degrees Celsius, reaction 40-50 hour, and making its polymerization generate solid content is 10-15 grams/100 milliliters and viscosity are more than or equal to that 8000cp, number-average molecular weight are 50000～76000, molecular weight distributing index < 1.4Polyamic acid solution; React as follows:
3. produce according to claim 2 the preparation method of the polyamic acid of flexible glue-free copper coated plate for two-layer method, its spyLevy and be, solvent for use is that water content is lower than 100ppm through the DMF of molecular sieve dehydration processing.
4. produce according to claim 2 the preparation method of the polyamic acid of flexible glue-free copper coated plate for two-layer method, its spyLevy and be, described aromatic tetrahydric dianhydride is pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '---and benzophenone tetracidOne in dianhydride and 4-4 Biphenyl Ether dianhydride.
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| CN107556501A (en) * | 2017-08-23 | 2018-01-09 | 中国科学院理化技术研究所 | A kind of polyimide film and its preparation method and application |
| CN111479395A (en) * | 2017-07-28 | 2020-07-31 | 中国地质大学（北京） | Preparation method of glue-free flexible copper-clad plate |
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