CN201307968Y - Double-sided flexible copper-clad plate - Google Patents
Double-sided flexible copper-clad plate Download PDFInfo
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- CN201307968Y CN201307968Y CNU2008202142153U CN200820214215U CN201307968Y CN 201307968 Y CN201307968 Y CN 201307968Y CN U2008202142153 U CNU2008202142153 U CN U2008202142153U CN 200820214215 U CN200820214215 U CN 200820214215U CN 201307968 Y CN201307968 Y CN 201307968Y
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- copper
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- copper foil
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Abstract
The utility model relates to a double-sided flexible copper-clad plate, comprising: a single-sided copper-clad plate, an adhesive layer coating on the single-sided copper-clad plate and another single-sided copper-clad plate pressing on the adhesive layer, the single-sided copper-clad plate comprises a copper foil and a polyimide layer coating on the copper foil, and the polyimide layer is adjacent to the adhesive layer. The dimensional stability, folding resistance and ageing resistance properties of the double-sided flexible copper-clad plate excel the double-sided copper-clad plate produced by the traditional three-layer method, the apparent mass excels the double-layer and double-sided copper-clad plate by a laminating method, and the utility model also has advantages of low cost and convenient mass production.
Description
Technical field
The utility model relates to a kind of double side flexible copper coated board, relates in particular to a kind of double side flexible copper coated board of slimming.
Background technology
Along with the slim lightweight of electronic product, require the also slim thereupon lightweight of circuit base material.Therefore the rigidity wiring board develops into flex circuit application or rigid-flexible combined circuit board.Particularly mobile phone needs large scale display, makes clamshell phone and slide phone in vogue.In order to pursue the connection reliability of renovating hinge part and slip lid, must make the base material of circuit have more slim and higher resistance to deflection, high-dimensional stability.In addition, LCD assembles requirement, and line bank has high dimensional stability and ultra-thin low resilience force, requires more slimming and have higher dimensional stability of base material.The traditional manufacture method of flexible polyimide copper clad lamination is three layers the glue type, it is to be coated with modified epoxide resin adhesive or the acrylate adhesive that last layer thickness is 6-30 μ m on the polyimide film of commercially available 12.5-50 μ m, after oven dry and Copper Foil roll-in are compound, another side at polyimide film is coated with identical adhesive again, after the oven dry again with another Copper Foil pressing, carry out hot curing then and obtain the double side flexible copper coated board that insulating substrate thickness is 24.5-110 μ m.In general the thickness of this double side flexible copper coated board is owing to be subjected to the influence of polyimide film (commercialization generally has only the product of specification such as 12.5,25,50 μ m) and bondline thickness, be difficult to do thinlyyer, if glue-line is thinner, the caking property of glue-line is descended, and in general bondline thickness can not be lower than 6 μ m.For slimming, present most of manufacturer develops the two-layer method flexibility coat copper plate that does not use epoxy glue or acrylate adhesive, can make thickness thinner, now the minimal thickness of commercially produced product can reach 14 μ m, it is to apply thermoplastic polyimide layer or make laminated film at the Thermocurable polyimide laminar surface, obtain double side flexible copper coated board with Copper Foil in the high temperature pressing, this is two layers of no gum base materials of so-called laminating.Because tack coat is the thermoplastic polyimide adhesive, for reaching the soldering resistance requirement, necessarily require the fusing point of thermoplastic polyimide glue-line to surpass 260 ℃, therefore need a kind of compound press of high temperature hot-rolling that surpasses more than 260 ℃.Because the compound press cost of investment of high temperature is very high, production efficiency is low, cause the overall product cost higher, on the other hand, material is at continuous compound tense, Copper Foil or polyimide film moment contact high temperature roller owing to the reason of heat expansion is easy to make material production wrinkle or ripple, finally influence the surface quality of finished product.Therefore the cost of two layers of method double sided board is much higher than the three-layer process double sided board, and apparent being difficult to controlled.At present, though two layers of method double sided board have plurality of advantages, market is under the pressure of cost pressure, and manufacturer terminal still uses the three-layer process double sided board than more options.
The utility model content
The purpose of this utility model provides a kind of double side flexible copper coated board, three-layer process manufacturing double side flexible copper coated board be can overcome and slimming and the relatively poor deficiency of dimensional stability are difficult to, and the problem of the expensive and apparent difference of two-layer method flexibility coverlay, its excellent combination property, with low cost can be realized the slimming of base material.
According to above-mentioned purpose of the present utility model, a kind of double side flexible copper coated board is proposed, comprise: a single-side coated copper plate, coat the adhesive layer of this single-side coated copper plate and be overlaid on another single-side coated copper plate on the adhesive layer, described single-side coated copper plate comprises Copper Foil and coats polyimide layer on the Copper Foil, the adjacent setting of described polyimide layer and adhesive layer.
Wherein, described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m; The gross thickness of described double side flexible copper coated board is 16-75 μ.Described polyimide layer forms after by the polyamic acid imidization of coating on the Copper Foil, and thickness is 5-45 μ m; The preferred 5-25 μ of the thickness of described polyimide layer m.Described adhesive layer is modified epoxide resin adhesive or modified acrylic ester adhesion agent layer, and thickness is 6-35 μ m.
The beneficial effects of the utility model: dimensional stability, folding resistance and performance such as ageing-resistant are higher than the double face copper that traditional three-layer process is produced, and apparent mass is better than the two-layer double face copper of laminating (seeing table 1)
Double side flexible copper coated board of the present utility model has overcome three-layer process manufacturing double side flexible copper coated board and has been difficult to slimming and the relatively poor deficiency of dimensional stability, and the problem of the expensive and apparent difference of two-layer method flexibility coverlay, base material did not have ripple after it was etched into the fine rule road, can do accurate circuit, have ultra-thin and circuit board gold and point unrippled characteristics, and have excellent folding resistance, thermal endurance, anti-flammability and good processing properties, also have advantage cheaply simultaneously, be convenient to produce in enormous quantities.
Description of drawings
Below in conjunction with accompanying drawing,, will make the technical solution of the utility model and other beneficial effects apparent by embodiment of the present utility model is described in detail.
In the accompanying drawing,
Fig. 1 is the schematic diagram of double side flexible copper coated board of the present utility model.
Embodiment
One, double side flexible copper coated board
As shown in Figure 1, the double side flexible copper coated board 10 of the utility model second embodiment, comprise: a single-side coated copper plate, coat the adhesive layer 3 of this single-side coated copper plate and be overlaid on another single-side coated copper plate on the adhesive layer 3, described single-side coated copper plate comprises Copper Foil 1 and coats polyimide layer 2 on the Copper Foil 1, described another single-side coated copper plate comprises Copper Foil 5 and coats polyimide layer 4, described polyimide layer 2,4 and adhesive layer 3 adjacent settings on the Copper Foil 5.
Wherein, described Copper Foil can be electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m; Described polyimide layer forms after by the polyamic acid imidization of coating on the Copper Foil, and thickness is 5-45 μ m; Preferred 5-25 μ m.The preferred 5-25 μ of the thickness of described polyimide layer m; Described adhesive layer is modified epoxide resin adhesive or modified acrylic ester adhesion agent layer, and thickness is 6-35 μ m; The gross thickness of prepared double side flexible copper coated board is 16-75 μ m.
Two, the manufacture method of double side flexible copper coated board
The manufacture method of the utility model double side flexible copper coated board comprises the steps: step 1: the preparation of raw material: Copper Foil is provided and prepares polyamic acid and adhesive; Described adhesive is the adhesive of epoxy binder modified, acrylate adhesive or other type, and can be that fire-retardant, the halogen-free flameproof of halogen is arranged, and also can be not fire-retardant adhesive.Step 2: preparation single face flexibility coat copper plate: coating one deck polyamic acid on Copper Foil forms the single-sided polyimide flexibility coat copper plate after super-dry, high-temperature sub amination; Polyimide surface to the single face flexibility coat copper plate carries out corona treatment; Step 3: preparation double side flexible copper coated board: coating one deck adhesive on the polyimides face of a single face flexibility coat copper plate that makes, after drying with another single face flexibility coat copper plate through roll-in compound and solidify after make double side flexible copper coated board.Specifically details are as follows.
1, the preparation of raw material
1.1, polyamic acid composition
By tetracarboxylic acid anhydride compounds and diamine compounds be dissolved in DMAC or and nmp solvent in, in the proportion of the equivalent proportion 0.9-1.0 of acid anhydrides and amine, obtain polyamic acid solution 4-35 ℃ of following polymerization reaction.
1.2, modified epoxy resin composition
1.2.1 halogen-containing modified epoxy resin composition
Low bromine epoxy resin 10-40 weight portion;
High bromine epoxy resin 10-20 weight portion;
Nbr carboxyl terminal 15-30 weight portion;
Curing agent 5-15 weight portion;
Curing accelerator 0.05-1.5 weight portion;
Filler 20-100 weight portion;
Solvent: an amount of;
Above material mixing is evenly obtained modified epoxy resin composition.
1.2.2, the halogen modified epoxy resin composition
Phosphorous epoxy resin 30-60 weight portion;
End carboxylated nitrile rubber 15-30 weight portion;
Rubber modified epoxy resin 10-25 weight portion;
Curing agent 20-50 weight portion;
Curing accelerator 0.01-1.0 weight portion;
Antioxidant 0.01-1.0 weight portion;
Phosphonium flame retardant 5-30 weight portion;
Inorganic fire-retarded filler 0-100 weight portions;
Organic solvent is an amount of;
Above material mixing is evenly obtained modified epoxy resin composition.
1.3, acrylate modified resin combination
Acrylate copolymer 70-90 weight portion;
Epoxy resin 10-20 weight portion;
Curing accelerator 0.01-2 weight portion;
Other organic solvent of butanone or acetone is an amount of;
Above material mixing is evenly obtained the modified acrylic ester resin composition.
2, the making of flexibility coat copper plate
Above-mentioned composition is used for the preparation of two-sided Copper Foil flexibility coat copper plate by following technology.
Use coating equipment to be coated on above the Copper Foil polyamic acid composition of synthetic gained; make then and apply Copper Foil through 80-200 ℃ of online drying oven; remove DMAC and NMP organic solvent and dry compositions thus; using down at 330-380 ℃ has the high temperature oven of nitrogen protection that the polyamic acid that is coated on the Copper Foil is carried out imidization again; after the cooling; again polyimide surface is carried out corona treatment, obtain surface-treated single-sided polyimide flexibility coat copper plate.
Adopt the single-sided polyimide flexibility coat copper plate of above-mentioned gained, with coating equipment aforesaid adhesive (modified epoxy resin composition or halogen modified epoxy resin composition or acrylic acid modified resin combination) is coated on its surface treated polyimide surface, adopt traditional three-layer process flexibility coat copper plate manufacturing process, adhesive layer is removed organic solvent through 80-170 ℃ of online baking oven baking, make its coated semi solid state, under 60-100 ℃, carry out compound with another Copper Foil then, under 60-100 ℃, carry out compound with another single-sided polyimide flexibility coat copper plate again, progressively heating up under 80-170 ℃ makes adhesive layer finish curing again, obtains the double side flexible copper coated board of the utility model second embodiment.
The dry thickness of polyimide coating is usually in the 5-45 mu m range in the above-mentioned double side flexible copper coated board material, preferred 5-25 μ m; The thickness of adhesive coating is 6-35 μ m; Used Copper Foil can be rolled copper foil or electrolytic copper foil, and thickness is 9-70 μ m.
Survey its thermal endurance, anti-flammability, peel strength and folding resistance and etching ripple and existing double face copper at the above-mentioned flexibility double face copper of making and compare, further give to illustrate in detail and describe as following embodiment.
3, embodiment and performance comparison
3.1, the single-sided polyimide flexibility coat copper plate
(ODA) is dissolved in 1:1DMAC and nmp solvent with the diamines yl diphenyl ether; then under nitrogen protection; to be 0.998 BPDA anhydrides compounds such as (BPDA) with diamines yl diphenyl ether equivalent proportion, stir 8 hours down, and carry out polymerization reaction and obtain polyamic acid solution at 20 ℃.
Be coated in above-mentioned polyamic acid solution on the electrolytic copper foil of 18 μ m with coating equipment; thickness is 12 μ m; dried by the fire 3 minutes down at 160 ℃; be placed in then in the nitrogen protection baking oven, in 2 hours, temperature risen to 350 ℃, be incubated 5 minutes; be cooled to room temperature in 2 hours again; obtain the single-sided polyimide flexibility coat copper plate, handle with corona processor pair polyimide surface again, for future use.
3.2, the double-sided polyimide flexibility coat copper plate
Embodiment 1: adhesive adopts modified epoxy resin composition
Low bromine epoxy resin (marque 530, DOW chemical company makes) 39 weight portions; Synthetic rubber (Zeon Corporation makes for marque Nipol 1072, acrylonitrile content 27 quality %) 20 weight portions; Diamino-diphenyl sulfone 2.5 weight portions; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight portion; Aluminium hydroxide (average grain diameter is 1 to 5 μ m, and purity is more than 99%) 30 weight portions; Antioxidant (marque 1010, CIBA GEIGY Co. makes) 0.20 weight portion.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the single-sided polyimide flexibility coat copper plate of above-mentioned processing by glue spreader, the coating adhesive layer thickness is 13 μ m, put in 160 ℃ the baking oven heat drying again into 3 minutes, then that another single-sided polyimide flexibility coat copper plate of itself and above-mentioned processing is compound by roll-in, combined temp is 70 ℃, put 120-170 ℃ baking oven into and carry out the back by designing program and solidify being laminated with thing, make double side flexible copper coated board.
Embodiment 2: adhesive adopts the halogen modified epoxy resin composition
Phosphorous epoxy resin (marque XZ92530, epoxide equivalent 340g/eq, phosphorus content 3.0 quality %, Dow Chemical Company makes) 38 weight portions; Synthetic rubber (Zeon Corporation makes for marque Nipol1072, acrylonitrile content 27 quality %) 20 weight portions; Rubber modified epoxy resin (CVC Specialty Chemicals Inc. makes for marque Hy RK84, elastomer content 32 quality %) 16 weight portions; Phosphorus containing phenolic resin (Dow ChemicalCompany makes for marque XZ92741, phosphorus content 9 quality %) 26 weight portions; Diamino-diphenyl sulfone 2.0 weight portions; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.30 weight portion; Aluminium hydroxide (average grain diameter is 1 to 5 μ m, and purity is more than 99%) 30 weight portions; Antioxidant (marque 1010, CIBA GEIGY Co. makes) 0.20 weight portion.The solids content of regulating glue with butanone solvent is 40%, mixes and makes halogen-free epoxy resin composition.Be coated in said composition on the single-sided polyimide flexibility coat copper plate of above-mentioned processing by glue spreader, the coating adhesive layer thickness is 13 μ m, put in 160 ℃ the baking oven heat drying again into 3 minutes, then that another single-sided polyimide flexibility coat copper plate of itself and above-mentioned processing is compound by roll-in, combined temp is 70 ℃, put 120-170 ℃ baking oven into and carry out the back by designing program and solidify being laminated with thing, make double side flexible copper coated board.
Embodiment 3: adhesive adopts acrylate modified resin combination
Acrylate copolymer (marque SG-70L, long rapids Co., Ltd.) 80 part, brominated bisphenol A epoxy resin (marque 530A80, DOW chemical company system) 25 part, curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.20 weight portion, (average grain diameter is 1 to 5 μ m to aluminium hydroxide, purity is more than 99%) 30 weight portions, antioxidant (marque 1010, CIBA GEIGY Co. makes) 0.20 weight portion, with butanone furnishing solids content is 40%, stirs to obtain the modified acrylic ester resin composition.Be coated in said composition on the single-sided polyimide flexibility coat copper plate of above-mentioned processing by glue spreader, the coating adhesive layer thickness is 13 μ m, put in 160 ℃ the baking oven heat drying again into 3 minutes, then that another single-sided polyimide flexibility coat copper plate of itself and above-mentioned processing is compound by roll-in, combined temp is 70 ℃, put 120-170 ℃ baking oven into and carry out the back by designing program and solidify being laminated with thing, make double side flexible copper coated board.
Comparative example 1: the science and technology marque SF302 051513DRN 250A of GUANGDONG SHENGYI three-layer process double side flexible copper coated board, the thick fire retarding epoxide resin glue-line of PI dielectric film 12.5 μ m/13 μ m/18 μ m rolled copper foils.
Comparative example 2: the compound polyimide glued membrane (PIXIO 622) that Japanese clock deep pool 25 μ m are thick is compound under 350 ℃ with 18 μ m rolled copper foils, obtains not having glue double-sided polyimide flexibility coat copper plate.
The performance of double side flexible copper coated board of the present utility model such as following table 2:
Table 2
The method of testing of above characteristic is as follows:
Peel strength (PS) is tested the peel strength of metal cap rock according to IPC-TM-650 2.4.9 method.
Flammability (anti-flammability): measure according to UL94 vertical combustion method.
Anti-immersed solder is tested according to IPC-TM-650 2.4.13.
The etching ripple, with double face copper through big to respectively making the parallel circuit that the live width distance between centers of tracks is 3mm, observe basic unit and have or not corrugated.
Folding resistance carries out with reference to JIS C-6471, and test condition is 0.5Kg/0.8R, no coverlay.Whole etchings of Copper Foil of double sided board folding resistance, one side is done circuit and is tested.
Heat ageing: double sided board is etched into the figure circuit of peel strength, 150 ℃ of bakings after 7 days, the peel strength retention rate.
As from the foregoing, double side flexible copper coated board of the present utility model has overcome three-layer process manufacturing double side flexible copper coated board and has been difficult to slimming and the relatively poor deficiency of dimensional stability, and the problem of the expensive and apparent difference of two-layer method flexibility coverlay, base material did not have ripple after it was etched into the fine rule road, can do accurate circuit, have ultra-thin and circuit board gold and point unrippled characteristics, and have excellent folding resistance, thermal endurance, anti-flammability and good processing properties, also have advantage cheaply simultaneously, be convenient to produce in enormous quantities.
Above embodiment, be not that content to composition of the present utility model imposes any restrictions, every foundation technical spirit of the present utility model or composition composition or content all still belong in the scope of technical solutions of the utility model any trickle modification, equivalent variations and modification that above embodiment did.
Claims (6)
1, a kind of double side flexible copper coated board, it is characterized in that, comprise: a single-side coated copper plate, coat the adhesive layer of this single-side coated copper plate and be overlaid on another single-side coated copper plate on the adhesive layer, described single-side coated copper plate comprises Copper Foil and coats polyimide layer on the Copper Foil, the adjacent setting of described polyimide layer and adhesive layer.
2, double side flexible copper coated board as claimed in claim 1 is characterized in that, described Copper Foil is electrolytic copper foil or rolled copper foil, and thickness is 9-70 μ m.
3, double side flexible copper coated board as claimed in claim 1 is characterized in that, described polyimide layer forms after by the polyamic acid imidization of coating on the Copper Foil, and thickness is 5-45 μ m.
4, double side flexible copper coated board as claimed in claim 3 is characterized in that, the preferred 5-25 μ of the thickness of described polyimide layer m.
5, double side flexible copper coated board as claimed in claim 1 is characterized in that, described adhesive layer is modified epoxide resin adhesive or modified acrylic ester adhesion agent layer, and thickness is 6-35 μ m.
6, double side flexible copper coated board as claimed in claim 1 is characterized in that, the gross thickness of described double side flexible copper coated board is 16-75 μ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2008202142153U CN201307968Y (en) | 2008-12-02 | 2008-12-02 | Double-sided flexible copper-clad plate |
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| Application Number | Priority Date | Filing Date | Title |
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| CNU2008202142153U CN201307968Y (en) | 2008-12-02 | 2008-12-02 | Double-sided flexible copper-clad plate |
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| CN201307968Y true CN201307968Y (en) | 2009-09-09 |
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| CNU2008202142153U Expired - Lifetime CN201307968Y (en) | 2008-12-02 | 2008-12-02 | Double-sided flexible copper-clad plate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109219238A (en) * | 2017-07-03 | 2019-01-15 | 张文耀 | Using silica gel plate as the circuit board of substrate and its manufacturing method |
-
2008
- 2008-12-02 CN CNU2008202142153U patent/CN201307968Y/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109219238A (en) * | 2017-07-03 | 2019-01-15 | 张文耀 | Using silica gel plate as the circuit board of substrate and its manufacturing method |
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