CN1181512C - Electrolytic condenser case and its fabricating method - Google Patents
Electrolytic condenser case and its fabricating method Download PDFInfo
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- CN1181512C CN1181512C CNB991060903A CN99106090A CN1181512C CN 1181512 C CN1181512 C CN 1181512C CN B991060903 A CNB991060903 A CN B991060903A CN 99106090 A CN99106090 A CN 99106090A CN 1181512 C CN1181512 C CN 1181512C
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Abstract
A fabricating method of an electrolytic condenser case comprises steps of: heating an aluminum plate surface at a temperature range of 100 to 280 DEG C; coating at least one side of the heating aluminum plate with a two-layered structure polyester resin film composed of a lower acid-deformation polyester resin film, whose melting point is 240 DEG C or below and an upper crystalline biaxially oriented polyester resin film whose melting point is 250 DEG C or above, wherein the surface of the acid-deformation polyester resin faces the aluminum plate; slowing cooling at air or quickly cooling at water below 60 DEG C the resin laminated aluminum plate and then rolling the aluminum plate with the resin laminated layer being outer layer.
Description
Technical field
The present invention relates to a kind of electrolytic condenser case and manufacture method thereof, more specifically, relate to the electrolytic condenser case that a kind of employing one side or bilateral have the aluminium sheet manufacturing of the double-deck alkyd resin film of being made up of the anti-crystallographic axis mylar of 2-of crystallization, and manufacture method.
Background technology
Well known fact is, electrolytic capacitor is by forming oxide layer with electrolysis on the anode metal surface, and the material that draws and peripheral negative electrode in conjunction with preparation.This electrolytic capacitor generally is contained in the housing.
Along with the electronic component microminiaturization that is installed on the printed circuit board (PCB), electrolytic capacitor also is tending towards adopting the whole bag of tricks microminiaturization, shorter lead for example is set capacitor is connected with circuit board, or the capacitor bottom is directly contacted with circuit board.For reaching the compact texture that does not have inessential space, people consider the sheet electrolytic capacitor that capacitor body sidepiece and circuit board surface directly contact, to realize the high density structures without any inessential space.
These electrolytic capacitors design to such an extent that be covered with insulating barrier at the inner surface of housing, though like this since highdensity layout with microminiaturization capacitor films is contacted also with housing and short circuit can not occur.In this case, the insulating barrier that is located on the shell inner surface adopts organic coating.
Outer surface at housing is coated with the resin sleeve pipe, contacts the function reduction that causes to prevent because with other electron component, and indicates rated insulation voltage and capacity.Because microminiaturized, pitch tube more and more is difficult to be enclosed within on the outer surface of housing, and in the face of shrinkage, cracking, aging and so on problem, people are just studying the method that is pressed with the machine coating on the aluminum upper strata.
The method example that covers organic coating on aluminum comprises resinous coat and resin pressure layer, and its shortcoming is as follows:
1) although when the processing liner, done bonding closely, epoxy resin, alkyd resin, vinyl chloride resin coating process are disadvantageous, because coating is difficult to thickening and insulating properties is not enough, and can not be satisfactory for the electrolyte corrosion resistance that is used in electrolytic capacitor, make the coating composition that contains in the electrolyte from going out and making electrolyte rotten.
2) because the chemical characteristic of chloro resin is fine, and chloro resinous coat method can provide the electrolyte good anti-corrosion, but because chloro resin poor adhesion, coating is easy to come off.
3) the alkene family tree fat overlay film that has an isocyanates binding agent can obtain good anti-corrosion and insulating properties but closely bonding property is not enough.And this resin molding can come off about 100 ℃ because of the heat that electrolytic capacitor produces, even seldom come off when the processing liner.
4), can make this resin molding cracking in the excessive operation of rolling although the polyamide-based resins overlay film of the nylon 6 on the gluing aluminium sheet or 66 and so on has excellent electric insulating, thermal endurance and closely bonding property.For overcoming the problem that this uses the nylon characteristic, need carry out the heating second time 150 to 450 ℃ temperature range.
5) be the shortcoming that pvdc layer is pressed on the aluminium sheet that because the distinctive low elongation of vinyl chloride, vinyl chloride is easy to come off and ftracture in calendering processing with adhesive.Adopt the soft vinyl chloride of poor heat resistance to make it and to carry out capacitor attached to the heat treatment on the circuit board.
Because adhesive generally is diluted in the organic solvent, will discard remaining solvent behind the gluing or after the glue drying, produce environmental pollution problems.The hardness of gummed composition produces the problem of cracking in the not enough and liner processing of adhesiveness.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of electrolytic condenser case that improves close adhesion, insulating properties, thermal endurance and corrosion resistance, and help to reduce environmental pollution.
For reaching this purpose, a kind of method of producing the electrolytic capacitor shell is provided, comprise the following steps: 100 to 280 ℃ of temperature range heating surface of aluminum plate; By lower floor be fusing point to be lower than 240 ℃ sour modified polyester resin adipose membrane and upper strata be that fusing point is higher than on the hot sticky one side at least that is attached to hot aluminium sheet of double-layer polyester resin molding that 250 ℃ the anti-crystallographic axis polyester resin film of crystallization 2-forms, the surface of sour modified polyester resin is facing to aluminium sheet herein; In air slow cooling or in the water below 60 ℃ fast cold this resin laminated aluminium sheet, with the resin laminated side of aluminium sheet serve as then outside Rolling Aluminium Plate.
Aluminium sheet will be handled by chemical modification.Adhesive one of comprises in the following combination at least: contain the block interpolymers of epoxy resin of the mylar of weight 10-90% and weight 10-90% or epoxy resin that the mean molecule quantity that contains weight 70-99% is 5000-20000 and weight 1-30% the anhydride group curing agent resin or contain weight 70-90% mylar and the resin of the amino resins of weight 10-30%.
The present invention also comprises resin is sticked to the step that once more aluminium sheet is heated to 150-300 ℃ after the step of aluminium sheet.Polyester resin film is a polyethylene terephthaldehyde ester resin molding.The sour modified polyester resin adipose membrane of lower floor comprises the M-phthalic acid of equimolar acid composition 0.5-10%.
A kind of method of producing the electrolytic capacitor shell is provided again in addition, comprises step: 100 to 280 ℃ of temperature range heating surface of aluminum plate; The anti-crystallographic axis polyester resin film of crystallization 2-that the fusing point of gluing is higher than 250 ℃ sticks on the side of hot aluminium sheet, and resin molding glue applied side surface is facing to aluminium sheet herein; Fast cold this resin laminated aluminium sheet in the water below 60 ℃, or carry out the second time 200-300 ℃ of temperature range and heat; Resin laminated side with aluminium sheet is an outside Rolling Aluminium Plate then.
In the present invention, aluminium sheet will be handled by chemical modification.Adhesive one of comprises in the following combination at least: contain the block interpolymers of epoxy resin of the mylar of weight 10-90% and weight 10-90% or epoxy resin that the mean molecule quantity that contains weight 70-99% is 5000-20000 and weight 1-30% the anhydride group curing agent resin or contain weight 70-90% mylar and the resin of the amino resins of weight 10-30%.
Also a kind of electrolytic condenser case is provided in addition again, comprise: a double-layer polyester resin molding and an aluminium sheet, herein, the double-layer polyester resin molding is that to be lower than 240 ℃ sour modified polyester resin adipose membrane and upper strata be that fusing point is higher than 250 ℃ the anti-crystallographic axis polyester resin film of crystallization 2-and forms to fusing point by lower floor, herein, the double-layer polyester resin molding is attached to the one or both sides of aluminium sheet; Perhaps, the fusing point of one deck gluing is higher than the one or both sides that 250 ℃ the anti-crystallographic axis double-layer polyester of crystallization 2-resin molding sticks to aluminium sheet.
It is exemplary and indicative to should be appreciated that top blanket property explanation and following elaborating are, and claims of the present invention are further explained.
Now in detail with reference to the preferred embodiments of the invention.
At first, the method of producing electrolytic condenser case comprises the one or both sides that double-layer polyester resin molding heat posted are attached to aluminium sheet, herein the double-layer polyester resin molding by the fusing point of 2-10 micron thickness be lower than 240 ℃ and to present the adhering sour modified polyester resin adipose membrane of heat and upper strata be that fusing point is higher than 250 ℃ the anti-crystallographic axis polyester resin film of crystallization 2-and forms; The perhaps netted adhesive of coated on a side of polyester resin film or double-layer polyester resin molding, then the glue applied side of film is combined with the aluminium sheet on opposite, herein, adhesive is thermosetting resin adhesive or contains epoxy resin and the mixture of the resin glue of anhydride group curing agent or mylar and amino resins.
Aluminium sheet used herein has good calendering processability, is generally aluminium sheet or the almag of purity more than 95%.
Best, before the lamination process, in known chromate, phosphate or chromium phosphate solution, handled by known chemical modification, on the metal surface, form stable compound, with the adhesiveness of stiffened aluminium sheet to adhesive.
So the aluminium sheet of handling is heated to 100-280 ℃ earlier.When aluminium sheet is heated to when being lower than 100 ℃, the used hot adhesiveness mylar of the present invention reduces the adhesiveness of aluminium sheet.When aluminium sheet was heated to above 280 ℃ of temperature, the adhesiveness between aluminium sheet and the resin molding was perhaps enough strong, but the hot sticky attached resin film of lower floor can melt, and causes bubble between aluminium sheet and resin molding.And, because heat treatment needs high-power heating facility, and adhesiveness not with the proportional increase of heating-up temperature, heating-up temperature fixes on the scope of 100-280 degree.
Preferably, the anti-crystallographic axis polyester resin film of crystallization 2-is used to be laminated to the polyester resin film on the metallic plate, for metallic plate provides good anti-corrosion.
Yet because its fusing point height and poor adhesion, crystallization 2-is anti-, and the crystallographic axis polyester resin film is difficult to be laminated on the metallic plate.For overcoming this problem, and make polyester resin film be easy to be laminated at a lower temperature on the metallic plate, employing is lower than the double-layer polyester resin molding that the anti-crystallographic axis polyester resin film of crystallization 2-that 240 ℃ and the fusing point that presents adhering sour modified polyester resin adipose membrane of heat and upper strata 5-10 micron thickness be higher than 250 ℃ is formed by the fusing point of the 2-10 of lower floor micron thickness.
The anti-crystallographic axis mylar of the crystallization 2-film-strength on upper strata is high and transparent.For the not restriction of the anti-crystallographic axis polyester resin film of upper strata crystallization 2-, so long as the polyester that is produced by sodium acid carbonate and the polycondensation of D (dior) composition is just, and polyethylene terephthaldehyde ester and polyethylene naphthalenedicarboxylate aldehydo-ester the best.
Flexible ground, coating adhesive on the anti-crystallographic axis polyester resin film of crystallization 2-, bonding one or bilateral of the aluminium sheet of the coated face of the anti-crystallographic axis polyester resin film of crystallization 2-and heating then.
The low melting point acid modified polyester resin adipose membrane of lower floor is the terephthalic acid (TPA) modified polyester resin, wherein 05-10% mole acid ingredient is a terephthalic acid (TPA), preferably adopt the polyethylene terephthaldehyde ester copolymer that contains 0.5-10% mole terephthalic acid (TPA) in the sour composition, because polyethylene terephthaldehyde ester copolymer reduces hot shrinkage and has good hot adhesiveness.
When replacing terephthalic acid (TPA) in the sour modified polyester resin with M-phthalic acid, if the amount of M-phthalic acid is lower than 0.5% mole sour composition, just can not improve adhesiveness, yet, if the amount of M-phthalic acid is higher than 10% mole, resin molding meeting shrinkage in the molded heat treatment process step of carrying out after lamination, the result reduces the adhesion property between resin molding and aluminium sheet.
The aluminium sheet that its upper strata is pressed with polyethylene terephthaldehyde ester resin molding is suitable for doing electrolytic condenser case most, because polyethylene terephthaldehyde ester can hot shrinkage and because its anti-crystal orientation structure manifests good anti-corrosion.
The thickness of resin film scope is at the 5-40 micron, preferably, and the general thickness 10-25 micron of lower floor and upper layer film.If thickness is lower than 10 microns, insulating properties is just not enough; If thickness is higher than 40 microns, such resin molding just is not suitable at economic aspect.
For making resin molding and aluminium sheet lamination, the pressure of on the laminating roll that is provided with the heat resistant rubber lining, being scheduled to.Add a layer aluminium sheet requirement uniformly laminating roll is remained on stationary temperature for obtaining performance.
Laminated aluminium plate can carry out post bake 150-300 ℃ temperature, be intended to: circuit board when the capacitor of polyester resin lamination is arranged, preventing to have alkyd resin presses the insulating properties of the aluminium sheet capacitor casing of layer to reduce owing to the hot shrinkage of resin molding, if heating-up temperature is lower than 150 ℃, secondary heat treatment is difficult to increase hot adhesiveness; If heating-up temperature is higher than 300 ℃, film may damage.
Because (lower floor) adhesiveness layer obtains sclerosis by secondary heat treatment, tack is strengthened, might improve form electrolytic condenser case and housing attached to the thermal endurance in the heating steps on the circuit board with process adhesiveness.
As mentioned above, capacitor casing is painted can surface at capacitor on sign capacity and withstand voltage, this is difficult to realize in existing capacitor miniaturization technologies, and use at the offside of (lower floor) adhesiveness layer of resin molding has the resin molding of printed layers that capacitor is carried out classification for this reason.
Can apply a jacket layer in addition and protect printed layers.
Flexible ground for the processing close adhesion of reinforced polyester resin molding and aluminium sheet, is coated with netted adhesive at a side or the bilateral of polyester resin film, and the glue applied side of film is combined with the aluminium sheet on opposite.Here adhesive is a thermosetting resin adhesive, or contains the resin glue of epoxy resin and anhydride group curing agent, or polyester and amine resin mixture.
It is if coating resin glue can cause environmental pressure on the whole surface of resin molding that adhesive is coated with webbed reason, in the step of heat hardening adhesive, lose adhesive, also cause economic loss owing to increase the consumption of coating adhesive, and, cause that in the operation of rolling aluminium sheet and resin molding break away from because of plasticity decline along with the adhesive phase curing adhesive.
Only with the double-layer resin film and not during coating adhesive, the preparation electrolytic capacitor and electrolytic capacitor can the generation resin molding in attached to the heating steps on the circuit board come off.For addressing this problem, the present invention is by reticulating the adhesive coating, increase the adhesiveness and the processing characteristics of the lower floor's acid modified polyester resin adipose membrane that constitutes the double-layer resin film.
The adhesive that is coated on resin molding one or bilateral is a kind of thermosetting resin adhesive, it is composed as follows: the resin that contains block copolymer, this block copolymer comprises the polyester that carboxyl group is arranged at its two ends of 10-90% weight and the epoxy resin of 10-90% weight, or contain the epoxy resin of mean molecule quantity 5000-20000 and the resin of anhydride group curing agent, perhaps contain the resin of mylar and amine resin.This adhesive does not at room temperature have caking, and good adhesiveness is arranged under short time high temperature, and coating and thermal endurance are all good.
In the process of the resin laminated aluminium sheet of preparation employing adhesive, thermosetting resin adhesive, or contain the resin glue of epoxy resin and anhydride group curing agent, or the adhesive that contains polyester and amine resin is coated on by bunching dicarboxyl composition and D (dior) composition, particularly a side of the polyester film that obtains of polyethylene terephthalic acid (TPA) or polyethylene naphthalenedicarboxylate dioctyl phthalate combines with aluminium sheet then.
All there is the polyester of carboxyl to obtain by bunching binary acid and polyalcohol at two ends.The example of binary acid comprises phthalic acid, M-phthalic acid and terephthalic acid (TPA), and they are generally all stable to human body.
The example of polyalcohol comprises 1,2 ethylidene glycol, diethylene glycol (DEG), triethylene glycol, neopentyl alcohol and 1,4-butanediol.
The example of epoxy resin comprises bisphenol A epoxide resin, bisphenol F epoxy resin or aliphatic bifunctional epoxy resin, and bisphenol A epoxide resin most preferably.The mixed proportion of mylar and epoxy resin can be conceived to anticaking capacity, adhesiveness and with the reaction of the curing agent of adhesive and change most preferably 30: 70 or 70: 30.
As for the adhesive that adopts ring resin and anhydride hardener, if the mean molecule quantity of epoxy resin is lower than 5000, bonding strength just can not be satisfactory; And if the mean molecule quantity of epoxy resin is higher than 20000, can increases viscosity and cause the adhesive coating performance low.
The weight ratio of ring resin and anhydride hardener is lower than at 99: 1 o'clock, even at high temperature also want long-time hardening epoxy resin; The weight ratio of ring resin and anhydride hardener is higher than the sclerosis that can not improve epoxy resin at 70: 30 o'clock again.
The preference of anhydride hardener comprises thermosetting dehydration trimer acid curing agent, and the caking capacity after being conceived to be coated with by dehydration trimerization wine acid and derivative thereof, stabs octyl group as hot decynyl trimer acid or three and makes.
As for saying the adhesive of forming by mylar and amine resin, if the weight ratio of mylar and amine resin less than 90: 10, the sclerosis of adhesive will be heated to high temperature, and firm time is long; If weight ratio surpasses 70: 30, since overvulcanization, the plasticity variation.
The coating weight of adhesive is preferably 0.2-4.0g/m
2, 0.4-2.0g/m more preferably
2
If the coating weight of adhesive is lower than 0.4g/m
2, adhesive is difficult to be coated on equably on the whole surface of resin; If the coating weight of adhesive is higher than 2.0g/m
2, adhesiveness will reduce.
Resin laminated aluminium sheet slowly cools off or quench cooled in the warm water below 60 ℃ in air.Consider plasticity, preferably behind second heating step, carry out quench cooled.
Slowly cooling and quench cooled are known, and the sour modified polyester resin adipose membrane of individual layer generally is used for quench cooled, in the quench cooled process, prevent the resin molding lamination after the amorphous tagma further enlarge.
In other words and since from the heat transfer of aluminium sheet contact zone, resin molding changes amorphous layer into by crystal layer.Carry out quench cooled if do not hasten, all resins layer all can become non-crystal, thereby mechanical performance descends, the content sex change but strengthen with the close adhesion of aluminium sheet.
The degree of crystallization of resin molding behind the lamination (being crystal region and the ratio in amorphous tagma) is generally in the scope of 30-70%, keeping the plasticity and the nurse tree adipose membrane of resin molding, and the adhesiveness of enhancing and aluminium sheet.
At duplicature or do not have under the situation of coating adhesive on the general polyester resin film of hot-setting adhesive, generally carry out the secondary cooling processing, because be difficult to reach desired adhesiveness in the lamination in the first time, if adopt generally slowly cooling in air of adhesive in the case, to increase adhesiveness, if but adopted duplicature, then preferred quench cooled would be damaged to prevent outer membrane.
Surface with the resin molding lamination is the outside, the aluminium sheet of processing cooling and obtain electrolytic condenser case.
Embodiment
Illustrate according to electrolytic condenser case of the present invention and manufacture method thereof below with reference to some embodiments.
" embodiment 1 "
The thick aluminium sheet of 0.3mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 180-220 ℃ with induction furnace earlier, is sent to laminating roll then.At the same time, the netted thermosetting resin glue of lower surface coating at double-layer polyethylene terephthaldehyde ester resin molding, the block interpolymers glue that thermosetting resin adhesive promptly is made of the epoxy resin of the polyester that carboxyl group is arranged at its two ends of 10-90% weight and 10-90% weight, double-layer polyethylene terephthaldehyde ester resin molding is made up of the sour modification terephthaldehyde ester resin molding of the sour composition that contains 5-8 mole % M-phthalic acid and so on of lower floor and the anti-crystallographic axis polyethylene of the crystallization 2-terephthaldehyde ester resin molding on upper strata.The glue applied side of resin molding is laminated to one or bilateral of opposite aluminium sheet with laminating roll.Then, aluminium sheet in air slowly the cooling, or in the water below 60 ℃ quench cooled.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 2 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 200-240 ℃ with induction furnace earlier, is sent to laminating roll then.At the same time, at the lower surface coating epoxy resin netted, that contain mean molecule quantity 5000-20000 of double-layer polyethylene terephthaldehyde ester resin molding and the resin binder of anhydride group curing agent, coating weight is 02-2.0g/m
2, double-layer polyethylene terephthaldehyde ester resin molding is made up of the sour modification terephthaldehyde ester resin molding of the sour composition that contains 2-6 mole % M-phthalic acid and so on of lower floor and the anti-crystallographic axis polyethylene of the crystallization 2-terephthaldehyde ester resin molding on upper strata.The glue applied side of resin molding is laminated to one or bilateral of opposite aluminium sheet with laminating roll.Then, once more aluminium sheet be heated to 200-280 ℃ and in the water below 60 ℃ quench cooled.The resin bed jewelling that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 3 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 210-230 ℃ with induction furnace earlier, is sent to laminating roll then.At the same time, lower surface coating resin binder netted, that contain mylar and amine resin at double-layer polyethylene terephthaldehyde ester resin molding, double-layer polyethylene terephthaldehyde ester resin molding is by the sour modification terephthaldehyde ester resin molding of the sour composition that contains 3-7 mole % M-phthalic acid and so on of lower floor, form with the anti-crystallographic axis polyethylene of the crystallization 2-terephthaldehyde ester resin molding on upper strata, the glue applied side of resin molding is laminated to one or bilateral of opposite aluminium sheet with laminating roll.Then, once more aluminium sheet be heated to 240-270 ℃ and in the water below 60 ℃ quench cooled.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 4 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 180 ℃ with induction furnace earlier, is sent to laminating roll then.The double-layer polyethylene terephthaldehyde ester resin film layer of being made up of the anti-crystallographic axis polyethylene of the crystallization 2-terephthaldehyde ester resin molding on the sour modification terephthaldehyde ester resin molding of the sour composition that contains 5-8 mole % M-phthalic acid and so on of lower floor and upper strata is pressed in one or bilateral of opposite aluminium sheet with laminating roll.Then aluminium sheet is slowly cooled off or quench cooled in the water below 60 ℃ in air.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 5 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 200 ℃ with induction furnace earlier, is sent to laminating roll then.The double-layer polyethylene terephthaldehyde ester resin film layer of being made up of the anti-crystallographic axis polyethylene of the crystallization 2-terephthaldehyde ester resin molding on the sour modification terephthaldehyde ester resin molding of the sour composition that contains 2-6 mole % M-phthalic acid and so on of lower floor and upper strata is pressed in one or bilateral of opposite aluminium sheet with laminating roll.Then aluminium sheet is slowly cooled off or quench cooled in the water below 60 ℃ in air.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated, finishes the electrolytic condenser case manufacturing.
" embodiment 6 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 230 ℃ with induction furnace earlier, is sent to laminating roll then.The double-layer polyethylene terephthaldehyde ester resin film layer of being made up of the anti-crystallographic axis polyethylene of the crystallization 2-terephthaldehyde ester resin molding on the sour modification terephthaldehyde ester resin molding of the sour composition that contains 3-7 mole % M-phthalic acid and so on of lower floor and upper strata is pressed in one or bilateral of opposite aluminium sheet with laminating roll.Then aluminium sheet is heated to quench cooled in 250 ℃ and the water below 60 ℃ again.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 7 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 170 ℃ with induction furnace earlier, is sent to laminating roll then.Simultaneously, with laminating roll a side scribble the thermosetting cement formed by 30: 70 to 70: 30 mylar of weight ratio and epoxy resin film, thick be that 25 microns polyethylene terephthaldehyde ester resin film layer is pressed in one or the bilateral that adds overheated aluminium sheet.Then aluminium sheet is slowly cooled off or quench cooled in the water below 60 ℃ in air.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 8 "
The thick aluminium sheet of 0.35mm (coiled material) surface that its bilateral all is covered with chromium phosphate is heated to 200 ℃ with induction furnace earlier, is sent to laminating roll then.By weight ratio be 95: 5 to 60: 4 mean molecule quantity 5000 to 20000 epoxy resin and contain resinoid that the curing agent of the ternary acid that dewaters forms be coated on 20 micron thickness a side of benzene dimethyl ester resin molding, the resin film layer of gluing is pressed in one or the bilateral that adds overheated aluminium sheet with laminating roll then.Then aluminium sheet be heated to again 240 ℃ and in air slowly cooling or in the water below 60 ℃ quench cooled.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 7 "
At first the surface of the thick aluminium sheet of 0.35mm (coiled material) is heated to 170 ℃, is sent to laminating roll then.Simultaneously, with laminating roll one side is scribbled and form polyethylene terephthaldehyde ester resin film layers thermosetting cement, 25 micron thickness by 30: 70 to 70: 30 mylar of weight ratio and epoxy resin film and be pressed in one or the bilateral that adds overheated aluminium sheet.Then aluminium sheet is slowly cooled off or quench cooled in the water below 60 ℃ in air.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 8 "
The thick aluminium sheet of 0.35mm (coiled material) surface is heated to 200 ℃ with induction furnace earlier, is sent to laminating roll then.By weight ratio be 95: 5 to 60: 4 mean molecule quantity 5000 to 20000 epoxy resin and contain thermoset adhesive that the curable agent of the ternary acid that dewaters forms be coated on 20 micron thickness a side of benzene dimethyl ester resin molding, the resin film layer of gluing is pressed in one or the bilateral that adds overheated aluminium sheet with laminating roll then.Then aluminium sheet be heated to again 240 ℃ and in air slowly cooling or in the water below 60 ℃ quench cooled.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" embodiment 9 "
At first, be sent to laminating roll then the surface of the thick aluminium sheet of 0.35mm (coiled material) is heated to 250 ℃.Use laminating roll simultaneously, a side is scribbled the thermoset adhesive be made up of the amine resin of 70-90% weight mylar and 10-30% weight and opposite side is provided with the sign condenser capacity and withstand voltage polyethylene terephthaldehyde ester resin film layers printed layers, 30 micron thickness are pressed in one or the bilateral that adds overheated aluminium sheet.Then aluminium sheet is slowly cooled off or quench cooled in the warm water below 60 ℃ in air.The resin laminated aluminium sheet that obtains like this is rolled up with resin laminated, finishes the electrolytic condenser case manufacturing.
" reference examples 1 "
The thick aluminium sheet of 0.3mm that its double-sided surface was handled with chromium phosphate applies epoxy thermosetting resin, and the resin laminated aluminium sheet that obtains like this is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" reference examples 2 "
Its double-sided surface all is heated to 270-300 ℃ with the thick surface of aluminum plate of 0.35mm that chromium phosphate was handled with induction furnace.With laminating roll polyamide resin is laminated on the aluminium sheet then.Resin laminated aluminium sheet is rolled up with resin laminated side, finishes the electrolytic condenser case manufacturing.
" reference examples 3 "
Its bilateral all is heated to 220-300 ℃ with the thick surface of aluminum plate of 0.35mm that chromium phosphate was handled with induction furnace.With laminating roll the polyamide resin that is coated with epoxy adhesive is laminated on the aluminium sheet then.Resin laminated aluminium sheet is resin laminated to be rolled up, finishes the electrolytic condenser case manufacturing.
Table 1 is depicted as the result that the resin laminated aluminium sheet that obtains is tested in embodiment 1 to 9 and reference examples 1 to 3.
" close adhesion test 1 "
According to the method for JISK6744 regulation, the interval with 1mm on plate shaped sample forms 100 cuttings, downcuts the sample of 6mm from its horizontal side.Sample conforms with does not have the standard that comes off and take place.
" close adhesion test 2 "
Each sample draws to prepare the electrolytic capacitor shell of the long 33mm of diameter 30mm with 2.5 extensibility.From investigating the close adhesion between resin molding and the aluminium sheet in appearance.
" corrosion resistance test "
Each sample rolls to prepare the electrolytic capacitor shell of the long 33mm of diameter 30mm with 2.5 elongation.Then electrolytic capacitor is dipped into overflowing with the assessment coating composition in the electrolyte.
＜insulating properties test 〉
Each sample rolls to prepare the electrolytic capacitor shell of the long 33mm of diameter 30mm with 2.5 elongation.Then electrolytic capacitor is dipped into that the three minutes Zhejiang with assessment copper (Cu) goes out in the solution that dissolves in 5g/l CuSO45H2O preparation in 5g/l hydrochloric acid.
＜heat-resistance test 1 〉
Each sample rolls to prepare the electrolytic capacitor shell of the long 33mm of diameter 30mm with 2.5 elongation.The top of housing is contacted with the hot plate that is heated to 250 ℃, and apply the load of 100 grams.The thermal endurance of housing is assessed by the dropping situations or the variation of housing top side.
＜heat-resistance test 2 〉
Each sample rolls to prepare the electrolytic capacitor shell of the long 33mm of diameter 30mm with 2.5 elongation.160 ℃ of heating 10 minutes, 250 ℃ of heating 5 minutes, 450 ℃ of heating 1 minute, the thermal endurance of housing is assessed by shrinkage, dropping situations and the variation of sample film housing.
[table 1] result of the test
| Close adhesion 1 | Close adhesion 2 | Corrosion resistance | Insulating properties | Thermal endurance 1 | Thermal endurance 2 | |||
| 160℃ | 250℃ | 450℃ | ||||||
| Embodiment 1 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| Embodiment 2 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 3 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| Embodiment 4 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 5 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 6 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ |
| Embodiment 7 | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 8 | ◎ | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Embodiment 9 | ◎ | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| Reference examples 1 | ○ | △ | ○ | ○ | ○ | ○ | ○ | △ |
| Reference examples 2 | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | ○ |
| Reference examples 3 | ○ | △ | ◎ | ◎ | ◎ | ○ | ○ | ○ |
(◎: very good, zero: good, △: common, *: bad)
Table 1 shows with reference examples and compares that electrolytic capacitor of the present invention has good close adhesion, insulating properties and thermal endurance with aluminium sheet.
As mentioned above, the present invention does not adopt the special sleeve pipe that is enclosed within on the electrolytic capacitor, contingent problem when having eliminated prior art and being covered with organic coating, and owing to do not need to discharge remaining solvent behind the coating adhesive, do not need dry adhesive yet, reduced environmental pollution.In addition, the present invention has fabulous close adhesion, corrosion resistance, electrical insulating property and thermal endurance, is specially adapted to electrolytic capacitor.
Those of ordinary skill in the art should be clear, under the prerequisite that does not depart from spirit of the present invention and category, can make various modifications and variations to the present invention, therefore, we think that the present invention contains that this invention provides, as to fall into appended claims and equivalent scope thereof modification and mutation.
Claims (11)
1. method of producing the electrolytic capacitor shell comprises step:
100 to 280 ℃ of temperature range heating surface of aluminum plate;
By lower floor be fusing point to be lower than 240 ℃ sour modified polyester resin adipose membrane and upper strata be that fusing point is higher than on the hot sticky one side at least that is attached to hot aluminium sheet of double-layer polyester resin molding that 250 ℃ the anti-crystallographic axis polyester resin film of crystallization 2-forms, the surface of sour modified polyester resin is facing to aluminium sheet herein;
In air slow cool down or in the water below 60 ℃ fast this resin laminated aluminium sheet of cooling; And
The rolling then resin laminated side with aluminium sheet is the aluminium sheet in the outside.
2. the method for claim 1 is characterized by, and aluminium sheet will be handled by chemical modification.
3. the method for claim 1 is characterized by, and also is included in resin is sticked to the step that again aluminium sheet is heated to 150-300 ℃ after the step on the aluminium sheet.
4. the method for claim 1 is characterized by, and the sour modified polyester resin adipose membrane of lower floor contains the M-phthalic acid of 0.5-10 mole % acid composition.
5. as each described method of claim 1 to 4, it is characterized by, be coated with netted adhesive rather than utilize heat bonding, the double-layer polyester resin molding is bonded on the aluminium sheet by lower surface at resin molding.
6. method as claimed in claim 5, it is characterized by, adhesive one of comprises in the following combination at least: contain the block interpolymers of epoxy resin of the mylar of weight 10-90% and weight 10-90% or epoxy resin that the mean molecule quantity that contains weight 70-99% is 5000-20000 and weight 1-30% the anhydride group curing agent resin or contain weight 70-90% mylar and the resin of the amino resins of weight 10-30%.
7. as each described method of claim 1 to 4, it is characterized by, polyester resin film is a polyethylene terephthaldehyde ester resin molding.
8. method of producing the electrolytic capacitor shell comprises step:
100 to 280 ℃ of temperature range heating surface of aluminum plate;
The fusing point of gluing is higher than on the one side at least that 250 ℃ the anti-crystallographic axis polyester resin film of crystallization 2-sticks to hot aluminium sheet, and the glue applied side of resin molding is facing to aluminium sheet herein;
In air slow cooling or in the water below 60 ℃ fast cold this resin laminated aluminium sheet; And
The rolling then resin laminated side with aluminium sheet is the aluminium sheet in the outside.
9. method as claimed in claim 8, it is characterized by, adhesive one of comprises in the following combination at least: contain the block interpolymers of epoxy resin of the mylar of weight 10-90% and weight 10-90% or epoxy resin that the mean molecule quantity that contains weight 70-99% is 5000-20000 and weight 1-30% the anhydride group curing agent resin or contain weight 70-90% mylar and the resin of the amino resins of weight 10-30%.
10. electrolytic condenser case comprises:
A double-layer polyester resin molding and an aluminium sheet, herein, the double-layer polyester resin molding is to be that fusing point is lower than 240 ℃ sour modified polyester resin adipose membrane by lower floor, with the upper strata be that fusing point is higher than the anti-crystallographic axis polyester resin film of 250 ℃ crystallization 2-and forms, herein, the double-layer polyester resin molding sticks to the one or both sides of aluminium sheet.
11. an electrolytic condenser case comprises:
The fusing point of one deck gluing that sticks to the one or both sides of aluminium sheet is higher than 250 ℃ the anti-crystallographic axis double-layer polyester of crystallization 2-resin molding.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980015771A KR19980033617A (en) | 1998-05-01 | 1998-05-01 | Method for manufacturing aluminum sheet for electrolytic capacitor exterior container and its articles |
| KR15771/98 | 1998-05-01 | ||
| KR15771/1998 | 1998-05-01 | ||
| KR24291/1998 | 1998-06-26 | ||
| KR1019980024291A KR19980065112A (en) | 1998-06-26 | 1998-06-26 | Manufacturing method and aluminum article for aluminum sheet for electrolytic capacitor exterior container |
| KR24291/98 | 1998-06-26 | ||
| KR38127/1998 | 1998-09-14 | ||
| KR1019980038127A KR19980087753A (en) | 1998-09-14 | 1998-09-14 | Laminating agent for electrolytic capacitor outer container and manufacturing method thereof |
| KR38127/98 | 1998-09-14 | ||
| KR1019980056965A KR19990037599A (en) | 1998-05-01 | 1998-12-18 | Electrolytic capacitor outer container |
| KR56965/1998 | 1998-12-18 | ||
| KR56965/98 | 1998-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1236963A CN1236963A (en) | 1999-12-01 |
| CN1181512C true CN1181512C (en) | 2004-12-22 |
Family
ID=27483277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991060903A Expired - Fee Related CN1181512C (en) | 1998-05-01 | 1999-05-04 | Electrolytic condenser case and its fabricating method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2000036443A (en) |
| CN (1) | CN1181512C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818935B2 (en) | 2001-09-12 | 2004-11-16 | Hynix Semiconductor Inc. | Semiconductor device and method for fabricating the same |
| KR100437124B1 (en) * | 2002-01-21 | 2004-06-22 | 주식회사 알펫 | Double layers resin film coated aluminium case for electronic device, method for manufacturing the aluminium case, and electronic device cased by the aluminium case |
| CN100380542C (en) * | 2004-05-28 | 2008-04-09 | 立隆电子工业股份有限公司 | Flame resisting capacitor |
| CN101339850B (en) * | 2008-06-10 | 2010-09-15 | 舟山市新龙电子设备有限公司 | Capacitor aluminum housing coating paint and coating process |
| CN105122403B (en) * | 2013-03-28 | 2019-05-03 | 日本贵弥功株式会社 | Electrolytic capacitor and its manufacturing method |
| KR101593114B1 (en) * | 2014-04-09 | 2016-02-11 | 이성동 | Biosensor |
| TWI727112B (en) * | 2017-10-31 | 2021-05-11 | 中國鋼鐵股份有限公司 | Manufacturing method of insulating aluminum material and insulating aluminum material, insulating aluminum shell and electronic component products |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6047103B2 (en) * | 1981-11-13 | 1985-10-19 | 東洋鋼鈑株式会社 | Manufacturing method of polyester resin film coated metal plate |
| GB8724238D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| JP3194591B2 (en) * | 1991-02-20 | 2001-07-30 | 株式会社神戸製鋼所 | Laminated aluminum material for electrolytic capacitor case |
-
1999
- 1999-05-04 CN CNB991060903A patent/CN1181512C/en not_active Expired - Fee Related
- 1999-05-06 JP JP11125442A patent/JP2000036443A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1236963A (en) | 1999-12-01 |
| JP2000036443A (en) | 2000-02-02 |
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