CN105644064A - Method for preparing flexible non-adhesive polyimide copper-clad plate through two-layer method - Google Patents
Method for preparing flexible non-adhesive polyimide copper-clad plate through two-layer method Download PDFInfo
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/0038—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving application of liquid to the layers prior to lamination, e.g. wet laminating
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/02—Temperature
- B32B2309/025—Temperature vs time profiles
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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Abstract
A method for preparing a flexible non-adhesive polyimide copper-clad plate through a two-layer method comprises the steps that 1, monomer aromatic diamine is dissolved in an N,N-dimethyl formamide solvent in a reaction kettle to be cooled to the temperature of -10 DEG C to -5 DEG C, aromatic dianhydride with equal molar ratios is added in batches within 5-10 hours, the low temperature is maintained for a reaction for 40-50 hours, and polymerization is performed to generate a polyamide acid solution with the solid content of 10-15 grams per100 milliliters, the viscosity larger than or equal to 8,000 cp, the number-average molecular weight of 50,000-76,000 and the molecular weight distribution index smaller than 1.4; a 0.2% thermal instability defoaming agent is added; copper foil is coated with the solution at the speed of 6-12 m/min and dried at the temperature of 100-160 DEG C to remove most of the solvent; next, the copper-clad plate is closely attached to the surface of a high-tension drying cylinder, dried at the speed of 1-5 m/min and the temperature of 180-200 DEG C to remove the remaining solvent completely, and rolled into rolls with the length of 1,000-2,000 m per roll; the rolls are placed in a special nitrogen high temperature oven and imidized at the temperature of 330-340 DEG C to obtain the flexible non-adhesive copper-clad plate, and the dimensional stability is within +/-5/10,000. The method can ensure high dimensional stability of the non-adhesive polyimide copper-clad plate, equipment is simple, and cost is low.
Description
Technical field
The present invention relates to flexible printed wiring board field, the method particularly relating to the flexible glue-free copper coated plate of two-layer method preparation.
Background technology
Polyimide copper clad lamination, with the property of interconnections of its uniqueness, obtains extensive use in the field such as telecommunication, computer, automobile, the whole world with 10%��15% annual rate of growth sustainable growth, within 2013, global consumption is more than 1,500,000,000 dollars. Having glue polyimide copper clad lamination at present due to its flexility, thermostability, dimensional stability is not good, and application is very limited. And glue-free polyimide copper clad lamination has glue polyimide copper clad lamination to compare with tradition, thermostability is greatly improved, and the region life-span of destroying or force to yield is greatly improved, and Rigid Flex achieves high density interconnection, substantially increases the link efficiency of circuit.
At present, external nearly all employing two-layer method produces glue-free system polyimide copper clad lamination, two-layer method is divided into again 4 kinds of manufacture methods according to different process, that is: the tape casting, metallikon, chemical plating/galvanoplastic and laminating, but said method is required for the special import equipment of costliness, cost height, complex process, speed is at 2-3m/min, and efficiency is low, energy consumption is high. Further, the dimensional stability of glue-free system polyimide copper clad lamination is a huge test. Polyimides to combine with copper, owing to the thermal coefficient of expansion (CET) of the two is different, it is being subject to cold and hot effect, when especially the precursor polyamic acid of polyimides being cooled down after high-temperature hot imidizate, warpage will be there is because of both not mating of thermal coefficient of expansion, even delamination of ftractureing, cause the poor dimensional stability of existing glue-free copper coated plate.
Summary of the invention
The technical problem to be solved in the present invention is to provide the novel processing step of a kind of high-dimensional stability that can guarantee that glue-free system polyimide copper clad lamination composite and equipment is simple, cost is low glue-free system polyimide copper clad lamination.
In order to solve above-mentioned technical problem, the invention provides to solve above-mentioned technical problem, the invention provides the method that two-layer method prepares flexible glue-free polyimide copper clad lamination, it is characterised in that step is as follows:
1) in a kettle., monomer aromatic diamines is dissolved in N, in dinethylformamide solvent, it is cooled to-10 degrees Celsius to-5 degrees Celsius, point 5��10 batches of addition total amounts and the equimolar aromatic tetrahydric dianhydride of monomer aromatic diamines in 5��10 hours, then maintain-10 degrees Celsius to-5 degrees Celsius, react 40-50 hour so that it is it is 10-15 gram/100 milliliters and the viscosity polyamic acid solution be more than or equal to 8000cp that polymerization generates solid content;React as follows:
Being obtained by reacting the polyamic acid solution of high molecular, low profile exponent, the number-average molecular weight of polyamic acid is 50000��76000, molecular weight distributing index < 1.4.
2) the polyimides acid solution obtained to above-mentioned steps adds the thermal instability deaeration agent of 0.2% weight percentage, after stirring, this solution is coated on Copper Foil 9��20 microns thick with the speed of 6-12m/min, at 100��160 degrees Celsius of dry removing major part solvents; The heat decomposition temperature of described thermal instability deaeration agent is lower than 300 degrees Celsius, in order to decompose completely when hot setting;
3) by step 2) copper-clad plate that obtains is fitted tightly on high-tension dryer surface with the speed of 1-5m/min, dries in 180��200 degrees Celsius, completely removes residual solvent; It is wound into the roll good of 1000��2000m/ volume;
4) roll good is put in special nitrogen high temperature oven, carries out imidizate under 330��340 degree, obtains two-layer method non-gel flexible copper-clad plate, and its dimensional stability is in �� 5/10000.
In described step 1) in, monomer aromatic diamines is preferably 3 kinds of material compositions:
3,4-diaminodiphenyl ether, p-phenylenediamine and molecular structure areCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5, and they proportionings are 2-6:2-6:1;
Solvent for use is the DMF processed through molecular sieve dehydration, and water content is lower than 100ppm; Aromatic tetrahydric dianhydride be pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '---benzophenone tetracarboxylic dianhydride and the one in 4-4 Biphenyl Ether dianhydride.
In described step 1) in, monomer aromatic diamines can also select 3,4-diaminodiphenyl ethers of 1:1-1:1.2 proportioning and the molecular structure to beCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5;
Solvent for use is the DMF processed through molecular sieve dehydration, and water content is lower than 100ppm; Aromatic tetrahydric dianhydride is pyromellitic acid anhydride.
In described step 1) in, monomer aromatic diamines can also adopt following 2 kinds of materials mixing:
P-phenylenediamine and molecular structure areCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5, and they proportionings are 1:1-1:1.2;
Solvent for use is the DMF processed through molecular sieve dehydration, and water content is lower than 100ppm; Aromatic tetrahydric dianhydride is pyromellitic acid anhydride.
Described step 2) in, during coating, the solvent of removing 60��90% is effective.
Described step 3) in, described drying cylinder is undertaken on coating line end, for diameter 1.5-2.5 rice, below static equilibrium 40g, the copper conduction oil cylinder body that can rotate around its axle center, cylinder surface is electroplate with layers of chrome thick for 0.08-0.1mm and does mirror process, uniform heating element heater in cylinder body, its cylinder surface temperature difference, within 3 degree, is undertaken on cylinder surface copper-clad plate high-tension and is thermally dried.
Described step 3) in roll good put into after in special nitrogen high temperature oven 400, first carry out baking oven intensification: rise to 180 degrees Celsius with the speed of 30 degrees Celsius/hour, then constant temperature 4 hours, then 2 hours rise to 330-340 degree Celsius; Constant temperature carries out imidizate in 1 hour again; Then temperature-fall period is carried out: be down to 270 degrees Celsius with the time of 1 hour, constant temperature 2 hours, within 2 hours, it is cooled to 200 degrees Celsius, then natural cooling, namely obtain the two glue-free polyimide copper clad laminations of layer method flexibility.
Described nitrogen high temperature oven 400 is top-opening type, including body of heater 10, the salable heat insulation furnace cover 20 in body of heater mouth, the vacuum system 40 for baking oven evacuation, for the inflated with nitrogen system of baking oven inflated with nitrogen, circulating fan system 60, power for baking oven, heating and cooling and carry out the control system of gas control;Also include the bin 70 being placed in furnace interior for unreeling dress polyimide copper clad lamination material volume 80;
Described body of heater 10 is vertical hollow circle tube, described body of heater 10 includes furnace shell 11, heat-insulation layer 12, outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15 from outside to inside successively, described outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15 constitute flue, and described bin 70 is placed in described flue;
Connect a hydraulicefficiency elevation structure 30 in described body of heater lateral wall, the lifting arm 33 on its top is laterally connected in the top of described heat insulation furnace cover 20, in order in body of heater top open part or opened it by described heat insulation furnace cover 20 lock sealing;
Described vacuum system 40 includes the vacuum pump 41 being placed in outside body of heater, and vacuum line 42 one end is communicated in vacuum pump, and the other end is communicated in described flue, and connector is provided with valve 43;
Described inflated with nitrogen system, including being opened in flue and can connect the air inlet 51 of body of heater external air source, air valve, pipeline;
Described circulating fan system 60 is by motor 61 and the fan blade 62 being connected to motor output end, and 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 connecting, and be connected to underframe top, the framework 72 that can accept multiple roll good forms.
Being provided with a circle groove 23 in the downside of described bell 20 and body of heater contact position, groove built with fluid sealant 21, in the periphery of fluid sealant, is respectively equipped with as the many water cooling tubes 22 of cooling effect fluid sealant on bell and body of heater.
The heating element heater 14 of described body of heater is heating wire, is provided with the through hole 151 of multiple heat transfer of being easy in flue space on the inner insulating layer 15 of body of heater.
Beneficial effects of the present invention is mainly described below:
For the dimensional stability of glue-free system polyimide copper clad lamination, the main way solved is to make the thermal coefficient of expansion of bi-material being combined with each other as far as possible close, and affect material thermal expansion coefficient (CTE) because have chemical constitution and two aspects of state of aggregation, after chemical constitution is determined, state of aggregation is then determined by more factor, for instance solvent for use, building-up process, coating method, drying program, imidizate program, annealing conditions etc.
1. the synthesis of polyamic acid
Polyamic acid is the precursor of polyimides, its chemical constitution directly determines the performance of polyimides, by MOLECULE DESIGN with repeatedly test correction, the molecular structure of the polyamic acid of present invention synthesis and copper coefficient of expansion CTE match, by introducing the characteristic functional group diamidogen containing glyoxaline structure, amine on imidazoles can form coordination with copper and be good for, and strengthens the connection with copper, thus the adhesive force that improve between finished product polyimide film and Copper Foil.
In the process of synthesis, due to by the reaction controlling low temperature state at-10 degrees Celsius to-5 degrees Celsius, the polymer of high molecular can be obtained, simultaneously, due to add aromatic tetrahydric dianhydride under long period interval, be gradually added into for point multiple times, making molecular weight distributing index lower than 1.4, these are very important for obtaining with the precursor polyamic acid of the polyimides of Copper Foil CTE match.
2. it is coated with and dry
The dry of the present invention is divided into two sections to carry out, and it is carry out while coating that first paragraph dries, and owing to being completely dried during without accomplishing and being coated with, this just can improving product gait of march on coating line so that the efficiency of coating is greatly improved; After polyamic acid coats copper foil surface, along with dry carrying out, coating process removes major part solvent, and in order to avoid follow-up aminating process has very big volume contraction, cause that Copper Foil deforms, therefore in coating process after polyamic acid surface drying, just carry out second segment to dry remaining solvent seasoning on the drying cylinder of high-tension with slightly higher temperature, the copper-clad plate after coating is made to fit tightly cladding dryer surface as far as possible, not only increase drying efficiency, also well prevent Copper Foil Texturized.Drying effect is as shown in Table 1.
Table one
| Dry above density (g/100cm2) | 1.832 | 1.82 | 1.812 | 1.834 | 1.816 |
| Dried surface density (g/100cm2) | 1.771 | 1.755 | 1.753 | 1.774 | 1.755 |
3. imidizate, annealing
In prior art, imidizate is complicated, speed is very slow, production capacity is low, the present invention devises special hot imidization technique and has simplified, special nitrogen high temperature oven carries out, imidizate has been controlled by accurate temperature programming, controlling to complete annealing in certain temperature again through programmed cooling, such guarantee copper-clad plate has good dimensional stability and higher peel strength.
Due to the fact that and have employed the production line researched and developed voluntarily, dividing Two stage dryer, second segment carries out on drying cylinder, re-uses special imidizate stove, whole production line is simplified, efficiency is high, production capacity is strong, and the glue-free polyimide copper clad lamination dimensional stability obtained is very good. Each performance indications are referring to shown in table three.
Accompanying drawing explanation
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 that two-layer method of the present invention prepares flexible glue-free polyimide copper clad lamination.
Fig. 2 is the 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, the two-layer method of the present invention prepares the production line of flexible glue-free polyimide copper clad lamination, the response system 100 including preparing polyamic acid solution successively, the coating system 200 that polyamic acid solution is applied to Copper Foil, by the high-tension drying cylinder 300 of the copper-clad plate redrying under high tension after coating, the special nitrogen high temperature oven 400 that roll good is carried out imidizate.
Described prepare the response system 100 of polyamic acid solution, coating system 200 can adopt equipment of the prior art, and wherein coating system 200 can adopt the equipment of existing coating applications; The parameter of high-tension drying cylinder 300 and special nitrogen high temperature oven 400 are then special designs of the present invention.
Described high-tension drying cylinder 300 is undertaken on coating system 200 end, the cylinder structure that paper industry uses can be adopted, the copper conduction oil cylinder body that such as can rotate around its axle center, but the present invention finds the necessary particular/special requirement of the Parameter Conditions to described drying cylinder through great many of experiments, for instance drying cylinder diameter, apparent condition, surface temperature difference scope, static equilibrium value etc. In the present embodiment, the drying section diameter that drying cylinder contacts with copper-clad plate is 1.5 meters, cylinder surface is electroplate with layers of chrome thick for 0.08-0.1mm and does mirror process, uniform heating element heater in cylinder body, its cylinder surface temperature difference, within 3 degree, is undertaken on cylinder surface copper-clad plate high-tension and is thermally dried. The static equilibrium of cylinder body requires at below 40g so that tension force is more uniform.
As in figure 2 it is shown, described nitrogen high temperature oven 400 include body of heater 10, the salable heat insulation furnace cover 20 in body of heater, the vacuum system 40 for baking oven evacuation, for the gas charging system of baking oven inflated with nitrogen, circulating fan system 60, power for baking oven, heating and cooling, gas control control system; Also include the bin 70 being placed in body of heater inner bottom part; Described body of heater 10 is vertical hollow circle tube, described body of heater 10 includes furnace shell 11, heat-insulation layer 12, outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15 from outside to inside successively, described outer thermal insulation layer 13, heating element heater 14, inner insulating layer 15 constitute flue, the heating element heater 14 of described body of heater is heating wire, in order in flue, temperature is more uniform, around furnace body inside wall, on inner insulating layer 15, it is provided with multiple through hole 151 being easy to heat transfer.The bin 16 being supported in bottom of furnace body it is provided with in described flue; A hydraulicefficiency elevation structure 30 is connected in described body of heater lateral wall, including the hydraulic cylinder 31 being connected to described body of heater side, the piston 32 of hydraulic cylinder is connected to the lower end of longitudinal extension bar 33, and the top, upper end of longitudinal extension bar 33 is fixedly connected on described lifting arm 33, thus being driven lifting arm to rise or fall by hydraulic piston 32, in order to described heat insulation furnace cover 20 lock sealing in body of heater top open part or is opened it. Described vacuum system 40 includes the vacuum pump 41 being placed in outside body of heater, and vacuum line 42 one end is communicated in vacuum pump, and the other end is communicated in described flue, and connector is provided with valve 43; Described nitrogen gas charging system (not entirely shown in figure, with reference to the nitrogen gas charging system of association area in prior art), including being opened in flue and can connect the air inlet 51 of body of heater external air source, air valve, pipeline; Described circulating fan system 60 is by motor 61 and the fan blade 62 being connected to motor output end, and described air intake leaf is two, is symmetricly set on the both sides of bottom of furnace body; Described bin 70 includes connecting the underframe 71 being supported in bottom of furnace body, and is connected to the framework 72 on underframe top, can accept multiple polyimide copper clad lamination material volume 80. In order to seal better, it is provided with a circle groove in the downside of described bell and body of heater contact position, groove is built with fluid sealant 21, in the periphery of fluid sealant, it is respectively equipped with on bell and body of heater as the many water cooling tubes 22 of cooling effect fluid sealant, in order to allow fluid sealant keep lower temperature to be unlikely to damage.
On this production line, the step preparing glue-free polyimide copper clad lamination by two-layer method is as follows:
1) in a kettle., by monomer aromatic diamines 3, 4-diaminodiphenyl ether, p-phenylenediamine and 3 kinds of materials of 2-(4-aminophenyl)-5-aminobenzimidazole are according to 2:2:1 mol ratio, it is dissolved in through molecular sieve dehydration process, water content is lower than the N of 100ppm, in dinethylformamide solvent, it is cooled to-10 degree left and right, point mole pyromellitic acid anhydride such as 5 batches of additions and diamidogen material total amount in 5 hours, maintain-10 degree left and right, react 40 hours, polymerization generates the polyamic acid solution that solid content is 15 grams/100 milliliters, the number-average molecular weight of the polyamic acid obtained is 51000��66000, molecular weight distributing index is < 1.4, for high molecular, the polyamic acid solution of low profile exponent.
2) in polyimide solution, the thermal instability deaeration agent that weight percentage is 0.2% is added, stir, described thermal instability deaeration agent refers to resolvent deaeration agent in heating process so that do not remain on the glue-free polyimide copper clad lamination in the end obtained. The thermal instability deaeration agent of the present invention adopts the special defoamer of TEGOAirex920 photocureable coating of Di Gao company, it would however also be possible to employ the TEGOFlow370 solvent-borne type levelling agent of Di Gao company, TEGOFlow300 solvent-borne type levelling agent or TEGOAirex940 solvent-borne type, no-solvent type coating deaeration agent.
3) by step 2) polyamic acid solution that obtains coats on Copper Foil 18 microns thick with the speed of 6m/min. Coating can adopt coating apparatus general in prior art, when being dried to removing 89% solvent with 140 degrees Celsius in the process of coating, then proceeds as follows,
3) dry in the speed of 180 degrees Celsius, 4m/min on special drying line, completely remove residual solvent, be wound into the web-like of 1000m/ volume.
4) roll good is put in special nitrogen high temperature oven, heats up with following process: rise to 180 degrees Celsius with the speed of 30 degrees Celsius/hour, then constant temperature 4 hours, within 2 hours, rises to 330 degrees Celsius; Then constant temperature carries out imidizate in 1 hour; Then temperature-fall period is carried out: be down to 270 degrees Celsius with the time of 1 hour by 330 degrees Celsius, constant temperature 2 hours, within 2 hours, it is cooled to 200 degrees Celsius, then namely natural cooling obtains two-layer method non-gel flexible copper-clad plate, and the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Embodiment 2
The content of embodiment 2 is roughly the same with embodiment 1. Institute the difference is that:
Step 1) in aromatic amine solution be 3 kinds of materials in embodiment 1, proportioning is 4:4:1, it is cooled to temperature for-8 degrees centigrade, in 8 hours, point 8 batches of additions wait mole bibenzene tetracarboxylic dianhydride, maintaining for-8 degrees centigrade response time is 45 hours, the polyamic acid obtained solid containing for 12 grams/100 milliliters, 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, and during coating, baking temperature is 130 degree, removes 81% solvent, step 4) in drying cylinder diameter be 2 meters, the temperature dried at high-tension dryer surface is 190 degrees Celsius, speed is 3m/min, and rolling is 1500m/ volume; According to the heating and cooling process of embodiment 1 during imidizate, in the middle of process, the constant temperature temperature of 1 hour is 335 degree, the non-gel flexible copper-clad plate obtained, and the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Embodiment 3
The content of embodiment 3 is roughly the same with embodiment 1. Institute the difference is that:
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, point 10 batches of additions wait mole 4-4 Biphenyl Ether dianhydride, maintaining-5 degrees Celsius of response time is 50 hours, the polyamic acid obtained solid containing for 13 grams/100 milliliters, molecular weight be 51000-64000, molecular weight distributing index is less than 1.4.
Step 2) in copper thickness be 12mm, during coating, baking temperature is 160 degree, and speed is 12m/min, removes 80% solvent; Step 4) in drying cylinder diameter be 2.5 meters, the temperature dried at high-tension dryer surface is 200 degree, speed is 2m/min, and rolling is 2000m/ volume; According to the heating and cooling process of embodiment 1 during imidizate, in the middle of process, the constant temperature temperature of 1 hour is 340 degree, the non-gel flexible copper-clad plate obtained, and the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Embodiment 4
Content in the present embodiment 4 is roughly the same with embodiment 3. Institute the difference is that:
Step 1) when preparing polyamic acid solution, the aromatic diamines of employing is 2 kinds of chemical substances: 3,4-diaminodiphenyl ethers and molecular structure areCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5, and its proportioning is 1:1. Used aromatic dianhydride is bibenzene tetracarboxylic dianhydride. The polyamic acid obtained solid containing for 13.5 grams/100 milliliters, molecular weight be 50000-65000, molecular weight distributing index is less than 1.4; Coating temperature is 120 degrees Celsius, speed is 6m/min, removes 80% solvent; Be 3m/min, temperature in cylinder dried hourly velocity it it is 200 degrees Celsius; The non-gel flexible polyimide copper clad lamination obtained after amination, the result of various performances detection is in shown in Table three.Separately, the data such as experiment parameter are with reference to table two.
Embodiment 5
Content in the present embodiment 5 is roughly the same with embodiment 4. Institute the difference is that:
The aromatic diamines adopted is that 2 kinds of chemical substances are identical with embodiment 4, and its proportioning is adjusted to 1:1.1. The polyamic acid obtained solid containing for 12.8 grams/100 milliliters, molecular weight be that 51000-68000, molecular weight distributing index are less than 1.4; Be 2m/min, temperature in cylinder dried hourly velocity it it is 180 degrees Celsius; The non-gel flexible polyimide copper clad lamination finally obtained, the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Embodiment 6
Content in the present embodiment 6 is roughly the same with embodiment 4. Institute the difference is that:
The aromatic diamines adopted is 2 kinds of chemical substances, and identical with embodiment 4, its proportioning is adjusted to 1:1.2. The polyamic acid obtained solid containing for 14 grams/100 milliliters, molecular weight be 51000-67000, molecular weight distributing index is less than 1.4; Be 4m/min, temperature in cylinder dried hourly velocity it it is 180 degrees Celsius; The non-gel flexible polyimide copper clad lamination finally obtained, the result of various performances detection is in shown in Table three. 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, institute the difference is that, the aromatic diamines of employing is 2 kinds of chemical substances: p-phenylenediamine and molecular structure areCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5, and its proportioning is 1:1. Used tetracarboxylic dianhydride is 3,3 ', 4,4 '---benzophenone tetracarboxylic dianhydride, the polyamic acid obtained solid containing for 11.6 grams/100 milliliters, molecular weight be 52000-69000, molecular weight distributing index is less than 1.4; The drying cylinder speed that second segment dries is 1m/min, temperature is 200 degrees Celsius; The non-gel flexible polyimide copper clad lamination finally obtained, the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Embodiment 8
Content in the present embodiment 8 is roughly the same with embodiment 7, and aromatic diamines adopts the chemical substance of same 2 kinds, and its proportioning is adjusted to 1:1.1. The polyamic acid obtained solid containing for 11 grams/100 milliliters, molecular weight be 52000-65000, molecular weight distributing index is less than 1.4; The non-gel flexible polyimide copper clad lamination finally obtained, the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Embodiment 9
Content in the present embodiment 9 is roughly the same with embodiment 7, and aromatic diamines adopts the chemical substance of same 2 kinds, and its proportioning is adjusted to 1:1.2. The polyamic acid obtained solid containing for 10.8 grams/100 milliliters, molecular weight be 53000-66000, molecular weight distributing index is less than 1.4; The non-gel flexible polyimide copper clad lamination finally obtained, the result of various performances detection is in shown in Table three. Separately, the data such as experiment parameter are with reference to table two.
Table two
Claims (10)
1. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination, it is characterised in that step is as follows:
1) in a kettle., monomer aromatic diamines is dissolved in N, in dinethylformamide solvent, it is cooled to-10 degrees Celsius to-5 degrees Celsius, point 5��10 batches of addition total amounts and the equimolar aromatic tetrahydric dianhydride of monomer aromatic diamines in 5��10 hours, then maintain-10 degrees Celsius to-5 degrees Celsius, react 40-50 hour so that it is it is 10-15 gram/100 milliliters and the viscosity polyamic acid solution be more than or equal to 8000cp that polymerization generates solid content; React as follows:
Being obtained by reacting the polyamic acid solution of high molecular, low profile exponent, the number-average molecular weight of polyamic acid is 50000��76000, molecular weight distributing index < 1.4.
2) the polyimides acid solution obtained to above-mentioned steps adds the thermal instability deaeration agent of 0.2% weight percentage, after stirring, this solution is coated on Copper Foil 9��20 microns thick with the speed of 6-12m/min, at 100��160 degrees Celsius of dry removing major part solvents; The heat decomposition temperature of described thermal instability deaeration agent is lower than 300 degrees Celsius, in order to decompose completely when hot setting;
3) by step 2) copper-clad plate that obtains is fitted tightly on high-tension dryer surface with the speed of 1-5m/min, dries in 180��200 degrees Celsius, completely removes residual solvent; It is wound into the roll good of 1000��2000m/ volume;
4) roll good is put in special nitrogen high temperature oven, carries out imidizate under 330��340 degree, obtains two-layer method non-gel flexible copper-clad plate, and its dimensional stability is in �� 5/10000.
2. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination according to claim 1, it is characterised in that in described step 1) in, monomer aromatic diamines is 3 kinds of materials:
3,4-diaminodiphenyl ether, p-phenylenediamine and molecular structure areCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5, and they proportionings are 2-6:2-6:1;
Solvent for use is the DMF processed through molecular sieve dehydration, and water content is lower than 100ppm; Aromatic tetrahydric dianhydride be pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '---benzophenone tetracarboxylic dianhydride and the one in 4-4 Biphenyl Ether dianhydride.
3. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination according to claim 1, it is characterised in that in described step 1) in, monomer aromatic diamines is 3,4-diaminodiphenyl ethers of 1:1-1:1.2 proportioning and molecular structure isCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5;
Solvent for use is the DMF processed through molecular sieve dehydration, and water content is lower than 100ppm; Aromatic tetrahydric dianhydride is pyromellitic acid anhydride.
4. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination according to claim 1, it is characterised in that in described step 1) in, monomer aromatic diamines is 2 kinds of materials:
P-phenylenediamine and molecular structure areCAS accession number is 2-(4-the aminophenyl)-5-aminobenzimidazole of 7621-86-5, and they proportionings are 1:1-1:1.2;
Solvent for use is the DMF processed through molecular sieve dehydration, and water content is lower than 100ppm; Aromatic tetrahydric dianhydride is pyromellitic acid anhydride.
5. the method that two-layer method according to any one of claim 1-4 prepares flexible glue-free polyimide copper clad lamination, it is characterised in that described step 2) in, remove the solvent of 60��90% during coating.
6. the method that two-layer method according to any one of claim 1-4 prepares flexible glue-free polyimide copper clad lamination, it is characterized in that, described step 3) in, described drying cylinder is undertaken on coating line end, for diameter 1.5-2.5 rice, below static equilibrium 40g, the copper conduction oil cylinder body that can rotate around its axle center, cylinder surface is electroplate with layers of chrome thick for 0.08-0.1mm and does mirror process, uniform heating element heater in cylinder body, its cylinder surface temperature difference, within 3 degree, is undertaken on cylinder surface copper-clad plate high-tension and is thermally dried.
7. the method that two-layer method according to any one of claim 1-4 prepares flexible glue-free polyimide copper clad lamination, it is characterized in that, described step 3) in roll good put into after in special nitrogen high temperature oven (400), first carry out baking oven intensification: rise to 180 degrees Celsius with the speed of 30 degrees Celsius/hour, then constant temperature 4 hours, then rise to 330-340 degree Celsius in 2 hours;Constant temperature carries out imidizate in 1 hour again; Then temperature-fall period is carried out: be down to 270 degrees Celsius with the time of 1 hour, constant temperature 2 hours, within 2 hours, it is cooled to 200 degrees Celsius, then natural cooling, namely obtain the two glue-free polyimide copper clad laminations of layer method flexibility.
8. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination according to claim 7, it is characterized in that, described nitrogen high temperature oven (400) is top-opening type, including body of heater (10), the salable heat insulation furnace cover in body of heater mouth (20), for baking oven evacuation vacuum system (40), for the inflated with nitrogen system of baking oven inflated with nitrogen, circulating fan system (60), power for baking oven, heating and cooling and carry out the control system of gas control; Also include the bin (70) being placed in furnace interior for unreeling dress polyimide copper clad lamination material volume (80);
Described body of heater (10) is vertical hollow circle tube, described body of heater (10) includes furnace shell (11), heat-insulation layer (12), outer thermal insulation layer (13), heating element heater (14), inner insulating layer (15 from outside to inside successively, described outer thermal insulation layer (13), heating element heater (14), inner insulating layer (15) constitute flue, and described bin (70) is placed in described flue;
A hydraulicefficiency elevation structure (30) is connected in described body of heater lateral wall, the lifting arm (33) on its top is laterally connected in the top of described heat insulation furnace cover (20), in order in body of heater top open part or opened it by described heat insulation furnace cover (20) lock sealing;
Described vacuum system (40) includes the vacuum pump (41) being placed in outside body of heater, and vacuum line (42) one end is communicated in vacuum pump, and the other end is communicated in described flue, and connector is provided with valve (43);
Described inflated with nitrogen system, including being opened in flue and can connect the air inlet (51) of body of heater external air source, air valve, pipeline;
Described circulating fan system (60) is by motor (61) and the fan blade (62) being connected to motor output end, and 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 connecting, and is connected to underframe top, can accept framework (72) composition of multiple roll good.
9. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination according to claim 8, it is characterized in that, it is provided with a circle groove (23) in the downside of described bell (20) and body of heater contact position, groove built with fluid sealant (21), in the periphery of fluid sealant, is respectively equipped with as the many water cooling tubes (22) of cooling effect fluid sealant on bell and body of heater.
10. the method that two-layer method prepares flexible glue-free polyimide copper clad lamination according to claim 8, it is characterized in that, the heating element heater (14) of described body of heater is heating wire, is provided with the through hole (151) of multiple heat transfer of being easy in flue space on the inner insulating layer (15) of body of heater.
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| CN107540840A (en) * | 2016-06-23 | 2018-01-05 | 臻鼎科技股份有限公司 | Polyamide acid, copper-clad plate and circuit board |
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| CN112477363A (en) * | 2020-11-17 | 2021-03-12 | 中国电子科技集团公司第四十六研究所 | Preparation method of low-warpage copper-clad plate |
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