CN105598014A - Amination device for preparing flexible adhesive-free polyimide copper-clad plate by two-layer method - Google Patents
Amination device for preparing flexible adhesive-free polyimide copper-clad plate by two-layer method Download PDFInfo
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- CN105598014A CN105598014A CN201610061761.7A CN201610061761A CN105598014A CN 105598014 A CN105598014 A CN 105598014A CN 201610061761 A CN201610061761 A CN 201610061761A CN 105598014 A CN105598014 A CN 105598014A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
- B05D3/0453—After-treatment
- B05D3/046—Curing or evaporating the solvent
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses an amination device for preparing a flexible adhesive-free polyimide copper-clad plate by a two-layer method. The amination device is a nitrogen high-temperature drying oven (400) independent of a polyamide acid coating and drying device; the nitrogen high-temperature drying oven (400) is provided with a top-openable furnace body (10); an insulation furnace cover (20) seals a furnace body opening; the amination device is also provided with a vacuum system (40), a nitrogen filling system, a circulating fan system (60), a control system for power supply, temperature raise and reduction and gas control of the drying oven, and a material rack (70) which is arranged inside the furnace body and is used for unreeling a material roll (80) filled with a polyimide copper-clad plate. The special nitrogen high-temperature drying oven disclosed by the invention is good in insulation effect and uniform in temperature; imidization can be finished by precisely controlling temperature rise and constant-temperature control, and annealing is finished at a certain temperature by cooling control, so that the copper-clad plate has good dimensional stability and higher peeling strength; meanwhile, compared with integrated equipment, the offline amination device disclosed by the invention has the advantages of low cost, high efficiency, low energy consumption and good amination effect.
Description
Technical field
The present invention relates to flexible printed wiring board field, relate in particular to two-layer legal system for the flexible glue-free copper that coversThe amination device of plate.
Background technology
Polyimide copper clad lamination is with its unique property of interconnections, in fields such as telecommunication, computer, automobilesObtain extensive use, the whole world is with 10%～15% annual growth sustainable growth, global consumption in 2013Exceed 1,500,000,000 dollars. There is at present glue polyimide copper clad lamination due to its flexility, heat resistance, size is steadyQualitative not good, application is very limited. And glue-free polyimide copper clad lamination and tradition have glue poly-Acid imide copper-clad plate comparison, heat resistance is greatly improved, and the region life-span of destroying or force to yield significantly improves, soft or hardBoard 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 methodMiddlely be divided into again 4 kinds of manufacture methods, that is: the tape casting, metallikon, chemical plating/electricity according to different processPlating method and laminating, but said method all needs expensive high, existing the establishing of special import equipment, costFor being roughly one amination curing apparatus, complex process, speed is slow, and efficiency is low, energy consumption is high. And,Glue-free is that the dimensional stability of polyimide copper clad lamination is a huge test. Polyimides is wanted and copperCombine, because the thermal coefficient of expansion (CET) of the two is different, be subject to cold and hot effect,Especially when the precursor polyamic acid of polyimides is cooling after high temperature hot-imide, will be because ofNot mating of both thermal coefficient of expansions and there is warpage, the even delamination of ftractureing, cause the existing glue-free copper that coversThe poor dimensional stability of plate. Operation above and good again, the last amination process place of the copper-clad plate obtainingManage and improperly also may cause that all that has been achieved is spoiled.
Summary of the invention
The technical problem to be solved in the present invention is to provide one can ensure that glue-free is that polyimide copper clad lamination is multipleTwo layers of legal system that high-dimensional stability and equipment are simple, cost is low of condensation material for glue-free be polyamides AsiaThe off-line amination device of amine copper-clad plate.
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, thisBright two-layer legal system is for the amination method of flexible glue-free polyimide copper clad lamination, and step is as follows: will be completelyRemoving rolling forms after residual solvent polyamic acid copper-clad plate web-like product puts into special nitrogen high temperature and driesIn case 400, first carry out baking oven intensification: rise to 180 degrees Celsius with the speed of 30 degrees Celsius/hour, soRear constant temperature 4 hours, then within 2 hours, rise to 330-340 degree Celsius; Constant temperature carries out imidizate for 1 hour again;Then carry out temperature-fall period: be down to 270 Celsius by the thermostat temperature of imidizate with the time of 1 hourDegree, constant temperature 2 hours, then within 2 hours, be cooled to 200 degrees Celsius, and then naturally cooling, obtain twoThe glue-free polyimide copper clad lamination of layer method flexibility, its dimensional stability is in ± 5/10000.
In order to realize this amination method, the invention provides a kind of special amination device, described aminationDevice is for being independent of the nitrogen high temperature oven 400 outside polyamic acid coating and drying device; Described nitrogenHigh temperature oven 400, baking oven is top-opening type, comprises body of heater 10, salable in the heat insulation furnace cover of body of heater mouth20, the vacuum system 40 that vacuumizes for baking oven, be inflated with nitrogen system, the circulating fan of baking oven inflated with nitrogenSystem 60, be baking oven power supply, heating and cooling and the control system of carrying out gas control; Also comprise and be placed in stoveBody inside is used for unreeling the bin 70 of dress polyimide copper clad lamination material volume 80;
Described body of heater 10 is vertical hollow circle tube, and described body of heater 10 comprises furnace shell from outside to inside successively11, heat-insulation layer 12, outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15, described outer thermal insulation layer13, heating element heater 14, inner insulating layer 15 form flue, and described bin 70 is placed in described flue;
Connect a hydraulicefficiency elevation structure 30 at described body of heater lateral wall, the lifting arm 33 on its top is horizontalBe connected in the top of described heat insulation furnace cover 20, so as by described heat insulation furnace cover 20 lock sealings in body of heaterTop open part or open it;
Described vacuum system 40 comprises the vavuum pump 41 that is placed in body of heater outside, and vacuum line 42 one end connectLead in vavuum pump, the other end is communicated in described flue, and connector is provided with valve 43;
Described inflated with nitrogen system, comprise be opened in flue and can be communicated with body of heater external air source air inlet 51,Air valve, pipeline;
Described circulating fan system 60 is by motor 61 and be connected in the fan blade 62 of motor output end,Described air intake leaf is two, is symmetricly set on the both sides of bottom of furnace body;
Described bin 70 is supported in the underframe 71 of bottom of furnace body by connection, and be connected to underframe top,The framework 72 that can accept multiple web-like products forms.
The present invention further provides the amination stove that has more sealing: at downside and the body of heater of described bell 20Contact position is provided with a circle groove 23, and fluid sealant 21 is housed in groove, in the periphery of fluid sealant, in bellWith on body of heater, be respectively equipped with the many water cooling tubes 22 that play cooling effect for fluid sealant.
The heating element heater 14 of described body of heater is heating wire, is provided with multiple on the inner insulating layer 15 of body of heaterBe convenient to the through hole 151 conducting heat to space in flue.
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 is to makeThe thermal coefficient of expansion of the bi-material interosculating approaches as far as possible, and affects material thermal expansion coefficient (CTE)Because have two aspects of chemical constitution and state of aggregation, chemical constitution determine after, state of aggregation byMore factor determines, for example solvent for use, building-up process, coating method, drying program, acylImidization program, annealing conditions etc.
Before amination of the present invention, the copper-clad plate front and continued drying effect of polyamic acid solution coating as shown in Table 1.
Table one
| Dry density (g/100cm above2) | 1.832 | 1.82 | 1.812 | 1.834 | 1.816 |
| Dry density (g/100cm below2) | 1.771 | 1.755 | 1.753 | 1.774 | 1.755 |
The present invention be by bone dry and without the Texturized copper-clad plate material of Copper Foil involve in row imidizate,Annealing. In prior art, imidizate complexity, speed are very slow, and production capacity is low, special nitrogen of the present inventionHigh temperature oven high insulating effect, temperature are even, can accurately control to heat up and thermostatic control completes acid imideChange, then be controlled at certain temperature by cooling and complete annealing, guarantee copper-clad plate has fine like thisDimensional stability and higher peel strength, meanwhile, off-line of the present invention (refers to and coating and dryOne) amination device is lower than the equipment cost of one, efficiency is high, energy consumption is little, amination is effective.
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 is for the production line of flexible glue-free polyimide copper clad lamination,Comprise successively and prepare the reaction system 100 of polyamic acid solution, polyamic acid solution is applied to Copper FoilCoating system 200, by coating after copper-clad plate redrying under high-tension high-tension drying cylinder 300,Web-like product is carried out to the special nitrogen high temperature oven 400 of imidizate.
Described reaction system 100, the coating system 200 of preparing polyamic acid solution can adopt prior artIn equipment, wherein coating system 200 can adopt the equipment in existing coating field; And high-tension drying cylinder400 of 300 parameter and special nitrogen high temperature ovens are special designs of the present invention.
Described high-tension drying cylinder 300 is undertaken on coating system 200 ends, can adopt paper industry to useDrying cylinder structure, for example can be around the copper conduction oil cylinder body of its axle center rotation, but the present invention is through a large amount of realIssue after examination and approval existing must particular/special requirement to the Parameter Conditions of described drying cylinder, for example drying cylinder diameter, surface state,Surface temperature difference scope, static balancing value etc. What in the present embodiment, drying cylinder contacted with copper-clad plate is dryPortion's diameter is 1.5 meters, and cylinder surface is electroplate with the chromium layer that 0.08-0.1mm is thick and does mirror process,Uniform heating element heater in cylinder body, its cylinder surface temperature difference, in 3 degree, is accepted copper-clad plate high-tensionCarry out heat drying in cylinder surface. The static balancing of cylinder body requires, below 40g, to make tension force moreAdd evenly.
As shown in Figure 2, described nitrogen high temperature oven 400 comprises body of heater 10, salable in the guarantor of body of heaterTemperature bell 20, the vacuum system 40 vacuumizing for baking oven, be gas charging system, the circulation of baking oven inflated with nitrogenFan system 60, be the control system of baking oven power supply, heating and cooling, gas control; Also comprise and be placed in stoveThe bin 70 of body inner bottom part; Described body of heater 10 is vertical hollow circle tube, described body of heater 10 from outward toInside comprise successively furnace shell 11, heat-insulation layer 12, outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15,Described outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15 form flue, the heating of described body of heaterElement 14 is heating wire, for temperature in flue is more even, around furnace body inside wall, interior heat insulationLayer 15 is provided with multiple through holes 151 of being convenient to heat transfer. In described flue, be provided with and be supported in bottom of furnace bodyBin 16; Connect a hydraulicefficiency elevation structure 30 at described body of heater lateral wall, described in comprising and being connected toThe hydraulic cylinder 31 of body of heater side, the piston 32 of hydraulic cylinder is connected in the lower end of longitudinal extension bar 33, andThe top, upper end of longitudinal extension bar 33 is fixedly connected on described lifting arm 33, thereby by hydraulic piston 32Drive lifting arm rise or decline so that by described heat insulation furnace cover 20 lock sealings in body of heater open topLocate or open it. Described vacuum system 40 comprises the vavuum pump 41 that is placed in body of heater outside, vacuum line42 one end are communicated in vavuum pump, and the other end is communicated in described flue, and connector is provided with valve 43; Described(complete illustrating not in figure, with reference to the nitrogen inflation system of association area in prior art for 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 system 60 is by motor 61 and be connected in the fan blade 62 of motor output end, described inAir intake leaf is two, is symmetricly set on the both sides of bottom of furnace body; Described bin 70 comprises that connection is supported inThe underframe 71 of bottom of furnace body, and be connected to the framework 72 on underframe top, can accept multiple polyimidesCopper-clad plate material volume 80. For sealing better, be provided with one in downside and the body of heater contact position of described bellCircle groove, is equipped with fluid sealant 21, in the periphery of fluid sealant, establish respectively on bell and body of heater in groovePromising fluid sealant plays the many water cooling tubes 22 of cooling effect, to allow fluid sealant keep lower temperature notAs for 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, are dissolved in through molecular sieve dehydrationProcess, in the DMF solvent of water content lower than 100ppm, be cooled to-10 degree leftThe right side, in 5 hours, points 5 batches add and mole pyromellitic acid anhydride such as diamines material total amount, dimensionBe held in-10 degree left and right, react 40 hours, polymerization generation solid content is the polyamide of 15 grams/100 millilitersAcid solution, the number-average molecular weight of the polyamic acid obtaining is 51000～66000, molecular weight distributing index is< 1.4, be the 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, makesOn the glue-free polyimide copper clad lamination that must in the end obtain, do not have residual. Thermal instability of the present invention is de-Infusion adopts the TEGOAirex920 photocureable coating dedicated defoamer of Di Gao company, also can adoptThe TEGOFlow370 solvent-borne type levelling agent of Di Gao company, TEGOFlow300 solvent-borne type levelling agentOr TEGOAirex940 solvent-borne type, no-solvent type coating defoamer.
3) by step 2) polyamic acid solution that obtains coats 18 micron thick with the speed of 6m/minCopper Foil on. Coating can adopt coating apparatus general in prior art, coating process in 140Degree Celsius be dried to while removing 89% solvent, then proceed as follows,
3) dry in 180 degrees Celsius, the speed of 4m/min on special drying line, remove surplus completelyRemaining solvent, is wound into the web-like that 1000m/ rolls up.
4) web-like product is put into special nitrogen high temperature oven, heats up: Celsius with 30 with following processDegree/hour speed rise 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; Then carry out temperature-fall period: with the time of 1 hour by 330Degree Celsius be down to 270 degrees Celsius, constant temperature 2 hours, is cooled to 200 degrees Celsius for 2 hours, then natureCoolingly obtain the copper-clad plate of two-layer method non-gel flexible, the results are shown in Table shown in three of various Performance Detection. Separately,The data such as experiment parameter are with reference to table two.
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, is cooled toTemperature is-8 degrees Celsius of left and right, and in 8 hours, points 8 batches mole bibenzene tetracarboxylic dianhydride such as add,Maintaining-8 degrees Celsius of left and right reaction time is 45 hours, and it is 12 grams/100 that the polyamic acid obtaining contains admittedlyMilliliter, molecular weight be 53000-69000, molecular weight distributing index is less than 1.4.
Step 2) in copper thickness be 12mm, coating speed is 9m/min, dry temperature when coatingDegree is 130 degree, remove 81% solvent, step 4) in drying cylinder diameter be 2 meters, at high-tension drying cylinderThe temperature of dry tack free is that 190 degrees Celsius, speed are 3m/min, and rolling is 1500m/ volume; Acid imideWhen change, according to the heating and cooling process of embodiment 1, in the middle of process, the constant temperature temperature of 1 hour is 335 degree,The non-gel flexible copper-clad plate obtaining, the results are shown in Table shown in three of various Performance Detection. Separately, experiment parameterEtc. data with reference to table two.
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 6:6:1 chilling temperatureFor-5 degrees Celsius, in 10 hours, points 10 batches mole 4-4 Biphenyl Ether dianhydride such as add, and maintain-5Degree Celsius reaction time is 50 hours, the polyamic acid obtaining solid containing being 13 grams/100 milliliter, pointsSon amount is 51000-64000, and molecular weight distributing index is less than 1.4.
Step 2) in copper thickness be 12mm, when coating, baking temperature is 160 degree, speed is12m/min, removes 80% solvent; Step 4) in drying cylinder diameter be 2.5 meters, at high-tension drying cylinderThe temperature of dry tack free is that 200 degree, speed are 2m/min, and rolling is 2000m/ volume; When imidizateAccording to the heating and cooling process of embodiment 1, in the middle of process, the constant temperature temperature of 1 hour is 340 degree, obtainsNon-gel flexible copper-clad plate, the results are shown in Table shown in three of various Performance Detection. Separately, the number such as experiment parameterAccording to reference to table two.
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 substance: 3,4-Diaminodiphenyl ether and molecular structure areCAS accession number is2-(4-aminophenyl)-5-aminobenzimidazole of 7621-86-5, its proportioning is 1:1. The fragrance two that usesAcid anhydride is bibenzene tetracarboxylic dianhydride. The polyamic acid obtaining admittedly containing be 13.5 grams/100 milliliters, molecular weightFor 50000-65000, molecular weight distributing index is less than 1.4; Coating temperature is 120 degrees Celsius, speedFor 6m/min, remove 80% solvent; In the time of cylinder dried, speed is that 3m/min, temperature are 200 CelsiusDegree; The non-gel flexible polyimide copper clad lamination obtaining after amination, various Performance Detection the results are shown in Table threeShown in. Separately, the data such as experiment parameter are with reference to table two.
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 polyamic acid obtaining is admittedly containing being that 12.8 grams/100 milliliters, molecular weight are that 51000-68000, molecular weight divideCloth index is less than 1.4; In the time of cylinder dried, speed is that 2m/min, temperature are 180 degrees Celsius; FinallyThe non-gel flexible polyimide copper clad lamination arriving, the results are shown in Table shown in three of various Performance Detection. Separately, realTest the data such as parameter with reference to table two.
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 into1:1.2. The polyamic acid obtaining admittedly containing be 14 grams/100 milliliters, molecular weight be 51000-67000,Molecular weight distributing index is less than 1.4; In the time of cylinder dried, speed is that 4m/min, temperature are 180 degrees Celsius;The non-gel flexible polyimide copper clad lamination finally obtaining, the results are shown in Table shown in three of various Performance Detection.Separately, the data such as experiment parameter are with reference to table two.
Embodiment 7
Content in the present embodiment 7 and embodiment 2 are roughly the same, and difference is, the fragrance of employingDiamines is 2 kinds of chemical substances: p-phenylenediamine (PPD) and molecular structure areCASAccession number is 2-(4-aminophenyl)-5-aminobenzimidazole of 7621-86-5, and its proportioning is 1:1. InstituteUsing tetracarboxylic dianhydride is 3,3 ', 4,4 '---and benzophenone tetracarboxylic dianhydride, it is 11.6 that the polyamic acid obtaining contains admittedlyGram/100 milliliters, molecular weight are 52000-69000, molecular weight distributing index is less than 1.4; Second segment is dryDry drying cylinder speed is that 1m/min, temperature are 200 degrees Celsius; The non-gel flexible polyamides Asia finally obtainingAmine copper-clad plate, the results are shown in Table shown in three of various Performance Detection. Separately, the data reference table such as experiment parameterTwo.
Embodiment 8
Content in the present embodiment 8 and embodiment 7 are roughly the same, and aromatic diamines adopts same 2 kindsChemical substance, its proportioning is adjusted into 1:1.1. Be 11 grams/100 millis solid the containing of the polyamic acid obtainingLiter, molecular weight are 52000-65000, and molecular weight distributing index is less than 1.4; Glue-free the scratching finally obtainingProperty polyimide copper clad lamination, the results are shown in Table shown in three of various Performance Detection. Separately, the number such as experiment parameterAccording to reference to table two.
Embodiment 9
Content in the present embodiment 9 and embodiment 7 are roughly the same, and aromatic diamines adopts same 2 kindsChemical substance, its proportioning is adjusted into 1:1.2. Be 10.8 grams/100 solid the containing of the polyamic acid obtainingMilliliter, molecular weight are 53000-66000, and molecular weight distributing index is less than 1.4; What finally obtain is glue-freeFlexible polyimide copper clad lamination, the results are shown in Table shown in three of various Performance Detection. Separately, experiment parameter etc.Data are with reference to table two.
Table two
Claims (3)
1. two-layer legal system, for the amination device of flexible glue-free polyimide copper clad lamination, is characterized in that, instituteStating amination device is the nitrogen high temperature oven (400) being independent of outside polyamic acid coating and drying device;Described nitrogen high temperature oven (400) is top-opening type, comprises body of heater (10), salable in body of heater mouthHeat insulation furnace cover (20), the vacuum system (40) vacuumizing for baking oven, be the inflated with nitrogen of baking oven inflated with nitrogenSystem, circulating fan system (60), be baking oven power supply, heating and cooling and the control system that carries out gas controlSystem; Also comprise that being placed in body of heater inside is used for unreeling the bin (70) that fills polyimide copper clad lamination material volume (80);
Described body of heater (10) is vertical hollow circle tube, and described body of heater (10) wraps from outside to inside successivelyDraw together furnace shell (11), heat-insulation layer (12), outer thermal insulation layer (13), heating element heater (14), inner insulating layer(15, described outer thermal insulation layer (13), heating element heater (14), inner insulating layer (15) form flue,Described bin (70) is placed in described flue;
Connect a hydraulicefficiency elevation structure (30), the lifting arm (33) on its top at described body of heater lateral wallBe laterally connected in the top of described heat insulation furnace cover (20), to described heat insulation furnace cover (20) is lockedBe sealed in body of heater top open part or open it;
Described vacuum system (40) comprises the vavuum pump (41) that is placed in body of heater outside, vacuum line (42)One end is communicated in vavuum pump, and the other end is communicated in described flue, and connector is provided with valve (43);
Described inflated with nitrogen system, comprises the air inlet that is opened in flue and can be communicated with body of heater external air source(51), air valve, pipeline;
Described circulating fan system (60) is by motor (61) and be connected in the fan blade of motor output end(62), described air intake leaf is two, is symmetricly set on the both sides of bottom of furnace body;
Described bin (70) is supported in the underframe (71) of bottom of furnace body by connection, and is connected to underframeTop, can accept framework (72) composition of multiple web-like products.
According to claim 1 two-layer legal system for the amination side of flexible glue-free polyimide copper clad laminationMethod, is characterized in that, is provided with a circle groove (23) in downside and the body of heater contact position of described bell (20),Fluid sealant (21) is housed, in the periphery of fluid sealant, be respectively equipped with as close in groove on bell and body of heaterSealing plays the many water cooling tubes (22) of cooling effect.
According to claim 2 two-layer legal system for the method for flexible glue-free polyimide copper clad lamination,It is characterized in that, the heating element heater (14) of described body of heater is heating wire, at the inner insulating layer (15) of body of heaterBe provided with multiple through holes (151) of conducting heat to space in flue be convenient to.
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| CN116714287A (en) * | 2023-08-08 | 2023-09-08 | 杭州锐健马斯汀医疗器材有限公司 | Heat treatment apparatus and heat treatment method suitable for absorbable material |
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| CN116714287A (en) * | 2023-08-08 | 2023-09-08 | 杭州锐健马斯汀医疗器材有限公司 | Heat treatment apparatus and heat treatment method suitable for absorbable material |
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| CN105598014B (en) | 2018-11-09 |
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