CN1805652A - Soft printing circuit board, multi-layer soft printing circuit board and portable telephone terminal - Google Patents
Soft printing circuit board, multi-layer soft printing circuit board and portable telephone terminal Download PDFInfo
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- CN1805652A CN1805652A CNA200610000573XA CN200610000573A CN1805652A CN 1805652 A CN1805652 A CN 1805652A CN A200610000573X A CNA200610000573X A CN A200610000573XA CN 200610000573 A CN200610000573 A CN 200610000573A CN 1805652 A CN1805652 A CN 1805652A
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- printed wiring
- layer
- flexible printed
- wiring board
- electric insulation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Structure Of Printed Boards (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a flexible printed wiring board and a multilayer flexible printed wiring board which prevent the adhesion of an FPC substrate of a bent part and which can hold a sufficient flexing resistance, in a method of laminating the board having a non-adhesive part and an adhesive part. The flexible printed wiring board includes at least an electric insulating layer and a conductor layer so that the ten-point average of the roughness of the above electric insulating layer front surface is 1.5 [mu]m or more to less than 2.0 [mu]m, and a contact angle is 60 DEG C or more to less than 120 DEG C, or ten-point average of the roughness is 2.0 [mu]m or more to less than 4.0 [mu]m, and two or more lamination of the flexible printed wiring board is performed. In the state which can be flexed and exposed, the electric insulation layer surfaces of the two or more flexible printed wiring boards counter, is in a non-adhesive state, and the part of the wiring board is laminated on the first multilayer printed wiring board and the second multilayer printed wiring board, respectively.
Description
Technical field
The present invention relates to flexible printed wiring board and multi-layer soft printing circuit board and use the portable telephone terminal that described multi-layer soft printing circuit board is arranged.
Background technology
In recent years, portable telephone terminal (below, be also referred to as portable phone) obtain popularizing rapidly.Along with popularizing of it, also constantly increase for the demand that with the miniaturization that realizes portable phone etc. is the flip type portable phone of purpose.Fig. 1 shows the skeleton diagram of flip-shell (collapsible) portable phone.As shown in Figure 1, the flip type portable phone comprises: first housing 10; Second housing 30; And articulated section 20, rotatably connect this first housing 10 and second housing 30 respectively.In addition, the flip type portable phone can rotate along the direction of arrow shown in Figure 1.
(below, be also referred to as the FPC substrate) has good flexibility, bendability because flexible printed wiring board, so, be widely used on the portable electric appts, particularly on the portable phone.
In addition, said here FPC substrate (below, be also referred to as three laminar substrates) be meant: the one or both sides at the electric insulation layer of for example polyimides etc. are provided with adhesive linkage, and lamination is pasted conductor layer such as Copper Foil for example and the substrate that forms, or paste, form on the conductor layer of circuit again that lamination is pasted cover layer at above-mentioned lamination and the substrate that forms, wherein, this cover layer comprises electric insulation layer, and the bond layer of polyimides for example etc.In addition, so-called double-deck FPC substrate (below, be also referred to as double layer substrate) is meant the substrate that solidifies behind the electric insulation layer of on such as the conductor layer of Copper Foil etc. coating polyimide etc., perhaps on the conductor layer that forms circuit again lamination paste tectal substrate.In addition, so-called multi-layer soft printing circuit board (below, be called the multi-layer FPC substrate) be meant: paste plural a plurality of FPC substrate or double layer substrate by adhesive linkage with various forms (variation) lamination, thus the circuit board that forms.
Here, Fig. 2 shows a wherein example that makes use-case that the FPC substrate is used for portable phone.As shown in Figure 2, FPC substrate 200 has following effect: be electrically connected circuit substrate 100 that is built in the housing 10 and the circuit substrate 300 that is built in the housing 30.
In recent years, be assembled in the circuit substrate in the portable phone, be accompanied by multifunction, the miniaturization of portable phone, the wiring density of its circuit substrate itself also can increase, thereby need carry out the multiple stratification of circuit substrate.Therefore, situation about describing below just increases to some extent: built-in in the housing 10,30, for example circuit substrate 100,300 is multiple stratification also, and the FPC substrate 200 that connects housing 10 and housing 30 also is to be formed by connecting by a plurality of FPC substrates.
Have as method of attachment: each housing is built-in with circuit substrate 100 and circuit substrate 300 respectively independently, across FPC substrate 200, connect this two circuit substrates by connector; And, circuit substrate 100,300 and FPC substrate 200 made the multi-layer FPC substrate of an integral body.
Here, Fig. 3 shows an example of multi-layer FPC substrate.
As shown in Figure 3, multi-layer FPC substrate 400 comprises with the lower part: circuit substrate 100; Circuit substrate 300; And the FPC substrate 200 between circuit substrate 100 and circuit substrate 300.In addition, in Fig. 3, omitted the diagram to circuit substrate 100, still, the structure of circuit substrate 100 is identical with the layer structure of circuit substrate 300, the circuit pattern difference.For example, the circuit substrate 300 of Fig. 3 is if six layers, and then circuit substrate 100 also is six layers, and still, circuit substrate 300 is different with 100 circuit pattern.
Circuit substrate 100 and 300 is that lamination is pasted a plurality of have tectal FPC substrate 70 (below, also only be called FPC substrate 70) and adhesive sheet 60 formation.FPC substrate 70 comprises FPC substrate 40 and cover layer 50, and wherein, this FPC substrate 40 comprises electric insulation layer 42, bond layer 41 and the conductor layer 43 that forms circuit, and this cover layer 50 covers this conductor layer 43.In addition, cover layer 50 comprises electric insulation layer 52 and bond layer 51.FPC substrate 200 generally is made of FPC substrate 70.
In order to realize densification, slimming, the multi-layer FPC substrate is the monolithic devices multi-layer FPC substrate that connecting portion is not set.
In addition, in order to ensure enough flexibilities (bendability), the sweep of monolithic devices multi-layer FPC substrate is not to be bonded between FPC substrate and the FPC substrate, but only lamination is pasted the circuit substrate part.
To disclose in the prior art in order can not being bonded with each other between the insulating barrier in the bend that makes such multi-layer soft circuit substrate, thereby to be provided with the structure (patent documentation 1) of disengaged portion.
But, in the manufacture method of monolithic devices multi-layer FPC substrate, because be by for example 140～200 ℃ * 20～50kgf/cm
2About heating and pressurizing handle and to carry out lamination and paste, so, even can produce, can't keep the problem (in other words, can't bring into play sufficient resistance to bend(ing) exactly) of sufficient flexibility not by also can be bonding mutually between the FPC of adhesive sheet, coupling part.In addition, in the prior art, in order to address this problem, every all needs by manpower bonding FPC strippable substrate.The problem that exists manufacturing cost to increase like this, again.
Patent documentation 1: the spy opens flat 7-312469 communique
Summary of the invention
In order to solve above-mentioned defective of the prior art, the object of the present invention is to provide a kind of comprise that non-bonded part divides and the laminating method of the substrate of bonding portion in, can prevent bend the FPC substrate bonding, also can keep the flexible printed wiring board and the multi-layer soft printing circuit board of sufficient resistance to bend(ing).
According to a first aspect of the invention, provide a kind of soft (flexibility) printed circuit board (PCB) as described below: comprise electric insulation layer and conductor layer at least, wherein, 10 mean roughness on this electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.Like this, even comprise that non-bonded part divides and the laminating method of the heat pressurization of the substrate of bonding portion, also because the concaveconvex shape and the surface functional group number on this electric insulation layer surface are less, thereby prevented that opposed this electric insulation layer surface is bonding, therefore, keep the flexibility of each flexible printed wiring board, improved resistance to bend(ing).
Preferred above-mentioned electric insulation layer is made of polyimides.Like this, even comprise that non-bonded part divides and the laminating method of the heat pressurization of the substrate of bonding portion, flexible printed wiring board also has sufficient thermal endurance and pliability.
According to a second aspect of the invention, provide a kind of flexible printed wiring board as described below: comprise electric insulation layer, bond layer and conductor layer at least, wherein, 10 mean roughness on this electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.Like this, even comprise that non-bonded part divides and the laminating method of the heat pressurization of the substrate of bonding portion, also because the concaveconvex shape and the surface functional group number on this electric insulation layer surface are less, thereby prevented that opposed this electric insulation layer surface is bonding, therefore, keep the flexibility of each flexible printed wiring board, improved resistance to bend(ing).
Preferred above-mentioned electric insulation layer is made of polyimides.Like this, even comprise that non-bonded part divides and the laminating method of the heat pressurization of the substrate of bonding portion, flexible printed wiring board also has sufficient thermal endurance and pliability.
According to a third aspect of the invention we, provide a kind of flexible printed wiring board as described below: cover layer is arranged at conductor layer, and wherein, this cover layer comprises bond layer, electric insulation layer; 10 mean roughness on this tectal electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m; And contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.Like this, even comprise that non-bonded part divides and the laminating method of the heat pressurization of the substrate of bonding portion, also because the concaveconvex shape and the surface functional group number on this electric insulation layer surface are less, thereby prevented that opposed this electric insulation layer surface is bonding, therefore, keep the flexibility of each flexible printed wiring board, improved resistance to bend(ing).
According to a forth aspect of the invention, a kind of multi-layer soft printing circuit board as described below is provided: lamination plural at least described flexible printed wiring board, be can be crooked state, and, the electric insulation layer surface of the plural flexible printed wiring board that exposes is opposed mutually, be non-adhering state, the part of this flexible printed wiring board is laminated to first multi-layer soft printing circuit board and second multi-layer soft printing circuit board respectively.Like this, keep the flexibility of this flexible printed wiring board, improved resistance to bend(ing).
According to a fifth aspect of the invention, a kind of portable telephone terminal that uses multi-layer flexible printed circuit board is provided, in the portable telephone terminal that comprises the articulated section that rotatably connects first housing and second housing, bend through multi-layer soft printing circuit board above-mentioned articulated section, fourth aspect, the electric insulation layer surface of the plural flexible printed wiring board that it exposes is opposite each other, is non-adhering state.Like this, keep the flexibility of this flexible printed wiring board, improved the resistance to bend(ing) of portable telephone terminal.
In addition, the invention provides a kind of metal-coated laminated board, be used for above-mentioned flexible printed wiring board or above-mentioned portable telephone terminal, wherein, at least comprise the conductor layer before electric insulation layer and circuit form, 10 mean roughness on this electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m; And contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
In addition, the invention provides a kind of cover layer, be used for the 3rd, the flexible printed wiring board or the above-mentioned portable telephone terminal of fourth aspect, constitute by bond layer and electric insulation layer, 10 mean roughness on this electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m; And contact angle is more than or equal to 60 ° and less than 120 °, and 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
In addition, the whole essential feature of the present invention is not enumerated in the design of foregoing invention, and combinations thereof also can become invention.
Description of drawings
Fig. 1 is the skeleton diagram of flip type portable phone.
The skeleton diagram that makes use-case when Fig. 2 is used for portable phone with the FPC substrate.
Fig. 3 is the sectional view of an example of multi-layer FPC substrate.
Fig. 4 is the sectional view of the flexible printed wiring board of first embodiment.
Fig. 5 is the sectional view of the flexible printed wiring board of second embodiment.
Fig. 6 is the sectional view of the flexible printed wiring board of the 3rd embodiment.
Fig. 7 is the sectional view of the multi-layer soft printing circuit board of the 4th embodiment.
Fig. 8 is the sectional view of the multi-layer soft printing circuit board of the 5th embodiment.
Fig. 9 is the key diagram of assay method of the surface contact angle of embodiment.
Figure 10 is the key diagram of the adhesive evaluation method of embodiment (double layer substrate).
Figure 11 is the key diagram of the adhesive evaluation method of embodiment (three laminar substrates).
Embodiment
Below, the present invention will be described by inventive embodiment.But the following examples also are not used in the related invention of qualification claim, and in addition, all combination of features that illustrate among the embodiment may not all be that technical solution problem of the present invention is necessary.
(flexible printed wiring board of first embodiment)
First embodiment of the invention provides a kind of like this flexible printed wiring board: comprise electric insulation layer and conductor layer at least, wherein, 10 mean roughness on this electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
Fig. 4 illustrates the sectional view of the flexible printed wiring board of first embodiment.
In Fig. 4, flexible printed wiring board 800 comprises conductor layer 820 and electric insulation layer 810.
Electric insulation layer 810 among first embodiment is the resin combination formation of neccessary composition with electrical insulating property resin 811 with filler 812.
In addition, the surface of electric insulation layer 810 forms the concaveconvex shape with following characteristics: 10 mean roughness are more than or equal to 1.5 μ m and less than 2.0 μ m, and contact angle is more than or equal to 60 ° and less than 120 °, and perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
Like this, when lamination is pasted a plurality of above-mentioned flexible printed wiring board, even comprise that non-bonded part divides and the utilization of the substrate of bonding portion 140～200 ℃ * 20～50kgf/cm for example
2About the laminating method of heating and pressurizing, also can be by adopting the flexible printed wiring board of said structure, thus prevent that opposed this electric insulation layer is bonded together, and therefore, has kept the flexibility of each flexible printed wiring board, and has improved resistance to bend(ing).
In addition, when being shaped under smaller or equal to above-mentioned heating-up temperature, for example other characteristics of circuit imbedibility, cementability reduction etc. are not given full play to.
The method that concaveconvex shape is set on these electric insulation layer 810 surfaces has: by described resin combination is set on conductor layer 820, thereby form the method (below, be also referred to as the filler additive process) of concaveconvex shapes on electric insulation layer 810 surfaces; Form after the electric insulation layer 810 on the conductor layer 820, for example utilize by the spraying fine-grain, make the sand-blast physical methods such as (Sandbalst) of surface configuration roughening, form the method (below, be also referred to as the surface roughening method) of concaveconvex shapes on electric insulation layer 810 surface.
The concaveconvex shape on electric insulation layer 810 surfaces of first embodiment of the invention forms by the filler additive process.
Can draw significantly by various experiments: in the filler additive process, the amount of the filler of interpolation can exert an influence to the concaveconvex shape of surface configuration.Addition with respect to electrical insulating property resin 100 weight portions behind the solidified forming, preferred filler 812 is 0.2～20 weight portion, and more preferably it is 0.2～10 weight portion.When the addition of filler 812 is during less than 0.2 weight portion, can't form sufficient concave-convex surface on the electric insulation layer surface, when the opposed electric insulation layer of heating and pressurizing, can be bonded together mutually between this electric insulation layer, thereby can't obtain sufficient flexibility, can not bring into play resistance to bend(ing).In addition, when more than or equal to 20 weight portions, can't bring into play for example needed characteristic of electrical characteristic etc.
The resin that electrical insulating property resin 811 adopts for example polyimides, polyamide, polyamide-imide resin etc. to have insulating properties is particularly considered from stable on heating angle, preferred polyimides.
Filler 812 adopts inorganic fine particles such as calcium monohydrogen phosphate, silicon, mica, aluminium oxide, particularly considers preferably phosphoric acid hydrogen calcium from the dispersiveness resin, crystal grain hardness equal angles.The particle diameter of filler is 0.5～5 μ m, considers preferred 1～3 μ m from the angle of manufacture views such as painting process.
Conductor layer 820 uses metal forming of for example copper, silver, aluminium etc. etc.About the thickness of metal forming, as long as be just not have problems within the employed thickness range in present technique field.
In addition, in the scope that various characteristics is reduced, can in above-mentioned resin combination, add various additives as required, for example adjust agent, coupling agent, defoamer etc.
The coating process of the above-mentioned electric insulation layer of present embodiment is to apply above-mentioned resin combination by coating methods such as scraper type coating (comma coater), mould coating (die coater), intaglio plate coatings on conductor layer, then, by the formation electric insulation layer that is heating and curing.
In addition, electric insulation layer can be the individual layer of the resin combination that is made of electrical insulating property resin and filler, perhaps also can be the layer that only is made of the electrical insulating property resin is set on conductor layer, the multilayer of this resin combination is set thereon again.
The surface roughening method can be to apply the electric insulation layer that is made of the electrical insulating property resin by above-mentioned coating process on conductor layer, after being heating and curing, makes the electric insulation layer surface form needed concavo-convex by sand-blast, wet blasting process, flushing processing etc.
Consider from the angle of the multiple stratification of FPC substrate, the thickness of preferred electric insulation layer 810 in 10～50 mu m ranges, more preferably 10～25 μ m.
(flexible printed wiring board of second embodiment)
Second embodiment of the invention provides a kind of flexible printed wiring board with following feature: be the flexible printed wiring board that comprises electric insulation layer, bond layer and conductor layer at least, wherein, 10 of this electric insulation layer surface mean roughness are more than or equal to 1.5 μ m and less than 2.0 μ m; And contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
Fig. 5 illustrates the sectional view of the flexible printed wiring board of second embodiment.
In Fig. 5, flexible printed wiring board 900 comprises that conductor layer 930, bond layer 920 and electric insulation layer 910 constitute.
The electric insulation layer 910 of second embodiment is made of electric insulating film, 10 mean roughness on electric insulation layer 910 surfaces are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
Like this, when lamination during this flexible printed wiring board of multilayer, even 140～200 ℃ * 20～50kgf/cm for example
2About heating and pressurizing, also can be by using the flexible printed wiring board of said structure, thus prevent that opposed this electric insulation layer is bonding, therefore, can keep the flexibility of each flexible printed wiring board, improve resistance to bend(ing).
Make electric insulation layer 910 surfaces become 10 mean roughness more than or equal to 1.5 μ m and less than 2.0 μ m, contact angle more than or equal to 60 ° and for example hydrophilic functional group's such as hydroxyl, carboxyl the method that do not import on the electric insulating film surface is arranged less than 120 ° method.Can list surface-treated methods such as not carrying out plasma treatment, corona treatment, coupling processing particularly.
Handle on the surface of the electric insulation layer 910 of the second embodiment of the present invention.In addition, also can implement surface treatment to the electric insulation aspect that is provided with bond layer one side in order to improve bonding force.
Handle according to this electric insulating film surface and can infer the following bonding structure in opposed electric insulation layer surface that is used to prevent.
In the prior art, in order to improve the adhesiveness of electric insulation layer and bond layer, pass through to implement the method that surface treatments such as plasma treatment, corona treatment import surface functional group (the especially hydrophilic functional group of carboxyl or hydroxyl etc.) electric insulation layer thereby adopted.This is to utilize surface functional group and the secondary aggregation keys such as chemical bond between the active function groups in the bonding agent constituent or hydrogen bond that import this insulating barrier, thereby improves fusible method.
In the present invention, opposed above-mentioned electric insulation layer with surface functional group, and when carrying out heating and pressurizing, can be bonding mutually between the above-mentioned layer, thereby, consider because pinning phenomenon can take place secondary aggegation key, infer the above-mentioned surface functional group that to be necessary as far as possible to reduce electric insulation layer.
In addition, the determination methods that has or not surface functional group among the present invention is to judge by contact angle, and promptly, under the few situation of the quantity of surface functional group, it is big that contact angle becomes, and on the contrary, under the many situations of quantity, contact angle diminishes.
As mentioned above, in the present embodiment, when 10 mean roughness on electric insulation layer surface during more than or equal to 1.5 μ m and less than 2.0 μ m, contact angle is more than or equal to 60 ° and less than 120 °.Even 10 mean roughness of above-mentioned laminar surface are more than or equal to 1.5 μ m and less than 2.0 μ m, if contact angle less than 60 °, will take place bonding when then carrying out heating and pressurizing with the form on opposed each surface of above-mentioned layer.
In addition, can adopt the surface of surface roughening method electric insulation layers 910 such as sand-blast, wet blasting process, flushing processing to be set to 10 mean roughness on this surface more than or equal to 2.0 μ m and less than 4.0 μ m.
In addition, above-mentioned surface roughness more than or equal to 2.0 μ m and situation less than 4.0 μ m under, when contact angle during less than 60 ° because concaveconvex shape is arranged, so can reduce contact area, thereby reduced the influence of surface functional group.Therefore, pinning phenomenon can not take place.
About bond layer 920, so long as the employed bonding agent in flexible printer circuit field is just passable, not special the qualification can be adopted epoxy resin as the bonding agent of base material etc.
Consider from the angle of the multiple stratification of FPC substrate, the thickness of preferred bond layer 920 in 5～50 mu m ranges, more preferably 10～25 μ m.
Electric insulation layer 910 adopts for example electric insulating films such as polyimide film, polyamide film, polyamide-imide resin film, poly (ether ether ketone) film.In addition, preferably have abundant thermal endurance and flexual polyimides.There is no particular limitation for the thickness of electric insulation layer, can carry out suitable selection according to the design of needed multi-layer FPC substrate.
Conductor layer 930 uses metal forming of for example copper, silver, aluminium etc. etc.There is no particular limitation for the thickness of metal forming, can carry out suitable selection according to the design of needed multi-layer FPC substrate.
The formation method of the flexible printed wiring board 900 of present embodiment is at the suitable adhesive-applying of conductor layer or electric insulation layer surface, electric insulation layer or conductor layer is set, thereby forms flexible printed wiring board.
As coating process, can suitably adopt scraper type coating, mould coating, intaglio plate coating etc. according to applied thickness etc.
(flexible printed wiring board of the 3rd embodiment)
Third embodiment of the invention provides a kind of flexible printed wiring board as described below: a kind of flexible printed wiring board that cover layer is arranged at conductor layer, wherein, this cover layer comprises bond layer, electric insulation layer, 10 mean roughness on this tectal electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
Fig. 6 illustrates the sectional view of the flexible printed wiring board of the 3rd embodiment.
In Fig. 6, will be arranged on the conductor layer by the cover layer 700 that electric insulation layer 710 and bond layer 720 constitute, wherein, conductor layer is formed with the circuit pattern of flexible printed wiring board of first embodiment or second embodiment etc.
A third embodiment in accordance with the invention, flexible printed wiring board is that the cover layer that will be made of bond layer and electric insulation layer is arranged on the conductor layer, wherein, 10 mean roughness on this electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
Like this, when lamination during a plurality of above-mentioned various flexible printed wiring board, even 140～200 ℃ * 20～50kgf/cm for example
2About heating and pressurizing, also can be by using the flexible printed wiring board of said structure, thus prevent that opposed this electric insulation layer is bonding, therefore, can keep the flexibility of each flexible printed wiring board, improve resistance to bend(ing).
Method, this method that preferred enforcement second embodiment is put down in writing make the surface of electric insulation layer 710 become the surface with following feature: 10 mean roughness are more than or equal to 1.5 μ m and less than 2.0 μ m; And contact angle is more than or equal to 60 ° and less than 120 °, and perhaps 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.And, the surface of this electric insulation layer 710 is handled.In addition, the surface treatment that also can be used to improve bonding force to the electric insulation layer enforcement that is provided with bond layer one side.
The formation method of cover layer 700 is suitable adhesive-applyings on electric insulation layer surface, and carries out heat drying, makes it be semi-cured state (below, also be called B level (stage)).Above-mentioned cover layer is arranged on the conductor layer with circuit pattern,, forms the flexible printed wiring board of the 3rd embodiment by being heating and curing.
As coating process, can suitably adopt scraper type coating, mould coating, intaglio plate coating etc. according to applied thickness etc.
About bond layer 720, so long as the employed bonding agent in flexible printer circuit field is just passable, not special the qualification can be adopted epoxy resin as the bonding agent of base material etc.
Consider from the angle of the multiple stratification of FPC substrate, the thickness of preferred bond layer 720 in 5～50 mu m ranges, more preferably 10～25 μ m.
Electric insulation layer 710 adopts for example electric insulating films such as polyimide film, polyamide film, polyamide-imide resin film, poly (ether ether ketone) film.In addition, preferably have enough thermal endurances and flexual polyimides.There is no particular limitation for the thickness of electric insulation layer, can carry out suitable selection according to the design of needed multi-layer FPC substrate.
(flexible printed wiring board of the 4th embodiment)
Fourth embodiment of the invention provides a kind of multi-layer soft printing circuit board as described below: lamination the flexible printed wiring board of plural at least the 3rd embodiment etc., be can be crooked state, and, the electric insulation layer surface of the plural flexible printed wiring board that exposes is opposed mutually, be non-adhering state, the part of this flexible printed wiring board is laminated on first multi-layer soft printing circuit board respectively and more than second on the flexible printed wiring board.
Fig. 7 illustrates the sectional view of the multi-layer soft printing circuit board of the 4th embodiment.In addition, in the following description, marked identical symbol for identical structure.
In Fig. 7, multi-layer soft printing circuit board 600 comprises first multi-layer soft printing circuit board 610 and second multi-layer soft printing circuit board 620 and flexible printed wiring board 630.
As required, this multi-layer soft printing circuit board 600 also can across (by) flexible printed wiring board 630 is provided with other multi-layer soft printing circuit boards outside the multi-layer soft printing circuit board 610,620.
Above-mentioned first, second multi-layer soft printing circuit board 610,620 can form like this: adhesive sheet 60 that can be by making glass cloth infiltration bonding agent, the prepregs that is semi-cured state or resin flake etc., with the flexible printed wiring board of a plurality of the foregoing descriptions of various patterns (pattern) lamination.
About above-mentioned flexible printed wiring board 630, two surfaces of the flexible printed wiring board of the foregoing description are electric insulation layer, and exposing by crooked state, the part of above-mentioned flexible printed wiring board is laminated on the above-mentioned multi-layer soft printing circuit board 610,620.In addition, the electric insulation layer of the above-mentioned flexible printed wiring board 630 of (more than or equal to two) is opposed respectively more than two, is set to non-adhering state.
The fourth embodiment of the present invention the provides a kind of lamination at least multi-layer soft printing circuit board of flexible printed wiring board of plural the 3rd embodiment etc., its be can be crooked state, and the electric insulation layer surface of the plural flexible printed wiring board that exposes is opposed, be in non-adhering state, the part of this flexible printed wiring board is laminated on respectively on first multi-layer soft printing circuit board and second multi-layer soft printing circuit board.
Like this, even 140～200 ℃ * 20～50kgf/cm for example
2About heating and pressurizing, can prevent that also a plurality of flexible printed wiring boards that can be crooked are bonded to each other, therefore, can keep the flexibility of each flexible printed wiring board, improve resistance to bend(ing).
(flexible printed wiring board of the 5th embodiment)
The invention provides a kind of in the portable telephone terminal that adopts multi-layer soft printing circuit board, it comprises the articulated section that rotatably connects first housing and second housing, this multi-layer flexible printed circuit board comprises the flexible printed circuit board of the 5th embodiment as described below: this flexible printed circuit board is through this articulated section, and be can be crooked state, and the electric insulation layer surface of the plural flexible printed wiring board that exposes is opposite each other, is non-adhering state.
Fig. 8 shows the structure chart through the multi-layer soft printing circuit board of the articulated section of portable telephone terminal of the 5th embodiment.In addition, in the following description, to the identical identical Reference numeral of structure mark.
In Fig. 8 (a), the flexible printed wiring board 630 by articulated section 20 is wound into a spiral helicine circle.
In Fig. 8 (b), be wound into the U font through the flexible printed wiring board 630 of articulated section 20.
Flexible printed wiring board according to a fifth embodiment of the invention, comprising that rotatably connecting first housing (is connected first housing and second housing with second housing, and first housing and second housing are rotated) the portable telephone terminal of articulated section in, be can be crooked state, and the electric insulation layer surface of the plural flexible printed wiring board that exposes is opposite each other, be non-adhering state, multi-layer soft printing circuit board with such flexible printed wiring board, as shown in Figure 8, under the state that has passed through the articulated section, has sufficient resistance to bend(ing), even, also can keep the flexibility of above-mentioned flexible printed wiring board so that repeat folding first housing and second housing.
Below, enumerate embodiments of the invention and experimental example, the present invention is described more specifically, still, embodiments of the invention do not carry out any qualification to the present invention.
(embodiment 1～5 and comparative example 1～3)
Surface roughness, contact angle, adherence, breakdown voltage to double layer substrate are estimated, and its result is as shown in table 1.
At first, the compound shown in the preparation table 1.It below is the details of each composition in the table 1.
Polyimide resin generates imide bond by the polyimide precursor resin that is heating and curing.As representational polyimide precursor resin polyamic acid is arranged.In addition, employed polyimide precursor resin is to make p-phenylenediamine (PPD) or comprise the diamines of its derivative and the aromatic tetracarboxylic acid reacts and the polyamic acid that obtains in present embodiment, the comparative example.
In addition, employed calcium monohydrogen phosphate, the peak value of its particle size distribution are 1～3 μ m (average grain diameter of filler is 1～3 μ m).When mixing polyimide precursor resin and calcium monohydrogen phosphate, add solvents such as N-N-methyl-2-2-pyrrolidone N-as required, and be adjusted to the viscosity that can be coated on the Copper Foil.The parts by weight of the polyimide resin after in addition, the parts by weight of the polyimide resin in the table 1 are represented to solidify.
The making of double layer substrate (laminated sheet of single face copper-surfaced)
Each resin combination that employing scraping article coating (bar coater) is formed shown in the coating table 1 on the roughened surface of rolled copper foil (strain formula meeting Mining マ テ リ ァ Le ズ manufacturing on community day, BHY, 18 μ m) is so that the thickness after its curing is 25 μ m.
In 80 ℃ to 150 ℃ temperature range, heating up 10 minutes interimly, thereby removing solvent.
Then, under nitrogen environment,, be cured in 180 ℃ to 400 ℃ temperature range, heated up three hours interimly.
Tectal making
On one side, implemented to use on the opposite one side of treated side of polyimide film (カ ネ カ Co., Ltd. make, ァ ピ カ Le 12.5 μ m) of predetermined processing (blasting treatment) scraping article be coated in normally used in the field such as flexible printed wiring board, be the resin combination of main component (cover layer usefulness) (for example, can use the spy to open disclosed resin combination such as 2001-15876 communique etc.) with epoxy resin, making its dried thickness is 25 μ m.
With 150 ℃ of heat dryings five minutes, carry out the B levelization after, on the resin combination face, paste separating film (manufacturing of リ Application テ Star Network Co., Ltd., release PET film, 38 μ m) by lamination.
In addition, when using separating film, peel off the back and use.
The making of flexible printed wiring board
On double layer substrate that has formed circuit or three laminar substrates, paste the cover layer adhesive side of having peeled off separating film, at 180 ℃ * 20kgf/cm
2Calendering formation under * 60 minutes the condition, thus flexible printed wiring board obtained.
(10 mean roughness)
Measuring instrument: use laser microscope (オ リ Application パ ス (Olympus) manufacturing, LEXT OLS300), calculate by following method of measurement.
(1) (in the present embodiment with the polyimides face as measurement face) faces up measurement and is placed on the objective table
(2), and aim at focus with 100 times of use lens of multiplying power.
(3) Top and the Bottom of Z-direction are set according to the brightness of image.
(4) irradiation 408nm laser and measure its reverberation, in the scope of X-direction 125 μ m, Y direction 96 μ m, the surface is scanned.
(5) cutoff value is set to 1/5, and calculates surface roughness (Rz) by the subsidiary parsing software of measuring instrument.
(surface contact angle)
The CA-X type of measuring instrument: Shi Yong Association and surface chemistry Co., Ltd. is measured by the following method.
Pure water 0.9 μ l (globule of diameter 0.9mm) is dropped on the measurement test portion.Confirm the pure water drip according to the cross section, and measure the height h and the diameter 2r of the globule as shown in Figure 9.The h that utilization is tried to achieve, r calculate contact angle θ by following formula.In addition, Fig. 9 is the sectional view of the globule that forms when dripping pure water.
tanθ1＝h/r θ＝2tan-1(h/r)
(adherence)
In double layer substrate, with two copper clad laminates of state lamination shown in Figure 10, at 180 ℃ * 20kgf/cm
2Roll under * 60 minutes the condition and handle and confirm.The polyimides face of the bilayer copper clad laminate that is made of the same resin constituent of each experimental example is opposed mutually, implement viscosity test.In addition, by the affirmation that range estimation is adhered, estimate based on following benchmark.Zero: not adhesion, *: adhesion.
(breakdown voltage)
The HVT-200-5 that uses the manufacturing of mountain water chestnut Electricity material society is made as 25mm Φ as measurement mechanism with electrode, in No. 2 insulating oils of JIS C 2320 (electric insulation oil) defined, boosts the value when judging insulation breakdown with 500V/sec.The test portion sheet is to have removed the conductor layer of substrate by etching method etc., and is cut into the square test portion sheet of 100mm.According to measurement result, estimate based on following benchmark.
Zero:, have the good insulation performance puncture voltage more than or equal to 200V/ μ m.
△:, have in the middle of reality is used the not breakdown voltage of in-problem grade more than or equal to 100 and less than 200V/ μ m.
Table 1
| | Comparative example 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 2 | Comparative example 3 | |
| Polyimide resin ※ 1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Calcium monohydrogen phosphate | 0.2 | 0.2 | 3 | 3 | 10 | 10 | 0 | 20 |
| Corona treatment | Be untreated | Handle | Be untreated | Handle | Be untreated | Handle | Be untreated | Be untreated |
| 10 mean roughness | 1.9 | 1.9 | 2.5 | 2.5 | 3.6 | 3.6 | 1 | 4.4 |
| Surface contact angle | 65° | 55° | 65° | 55° | 65° | 55° | 65° | 65° |
| Adherence | ○ | × | ○ | ○ | ○ | ○ | × | ○ |
| Breakdown voltage | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ |
※ 1: polyimide resin: make the polyamic acid after being heating and curing become polyimide resin 100 weight portions.
The unit of component (polyimide resin and calcium monohydrogen phosphate) is a weight portion.
The unit of 10 mean roughness is μ m.
(embodiment 6～8 and comparative example 4)
Surface treatment state, adherence to the polyimide film of three laminar substrates are estimated, and its result is as shown in table 2.In addition, the measurement that is not described in detail, evaluation method are identical with aforementioned content.
The making of three laminar substrates (single face copper clad laminate)
Implemented to use on the opposite one side of treated side of polyimide film (カ ネ カ Co., Ltd. make, ァ ピ カ Le 12.5 μ mNPI) of predetermined processing (blasting treatment) scraping article coating coating (substrate with) resin combination (for example can use the spy to open disclosed resin combination such as 2001-15876 communique etc.) at single face, and the thickness after it is solidified is 10 μ m, wherein, this resin combination often use in fields such as flexible printed wiring boards, with the resin combination of epoxy resin as main component.
150 ℃ of following heat dryings five minutes, carry out the B levelization after, stick on the resin combination face by lamination by the matsurface of lamination rolled copper foil (strain formula can Mining マ テ リ ァ Le ズ manufacturing on community day, BHY, 18 μ m).
In 40 ℃ to 200 ℃ temperature province, heated up three hours interimly, make above-mentioned resin combination full solidification, thereby obtain the single face copper clad laminate.
(adherence)
In three laminar substrates, with two copper clad laminates of state lamination shown in Figure 11, at 180 ℃ * 20kgf/cm
2Roll processing under * 60 minutes the condition and confirm that wherein, this copper clad laminate is to adopt the polyimides with various characteristics to make.The polyimides face of three layers of copper clad laminate will being made by each film is opposed mutually, implements viscosity test.In addition, by the affirmation that range estimation is adhered, estimate based on following benchmark.Zero: not adhesion, *: adhesion.
Table 2
| The film surface characteristic | Embodiment 6 | Embodiment 7 | Comparative example 4 | Embodiment 8 |
| 10 mean roughness (Rz) | 1.9 | 1.9 | 1.9 | 3.6 |
| Surface contact angle | 65° | 10°※2 | 55°※3 | 65°※4 |
| Adherence | ○ | ○ | × | ○ |
The unit of 10 mean roughness is μ m.
Below, the ※ mark in the his-and-hers watches 2 is elaborated.
※ 2: polyimide film is placed added micro-CF
4(carbon tetrafluoride) or C
2F
6Implemented plasma treatment in the nitrogen atmosphere of (hexafluoroethane).
※ 3: implemented corona treatment.
※ 4: implemented blasting treatment.
In addition, be to carry out surface treatment in the present embodiment by blasting treatment, still, in the present invention, surface treatment method is not limited especially.For example also can adopt other processing methods such as wet blasting process, flushing processing to carry out roughened.
Utilize possibility on the industry
The non-bonded part that comprises of doing in the present invention divides in the laminating method with the substrate of bonding portion, can prevent bonding, the flexible printed wiring board and multi-layer soft printing circuit board and the portable telephone terminal that keep sufficient resistance to bend(ing) of the FPC substrate of bend, have the possibility of utilizing on the industry.
Claims (9)
1. flexible printed wiring board, it is characterized in that: comprise electric insulation layer and conductor layer at least, wherein, 10 mean roughness on described electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and, contact angle is more than or equal to 60 ° and less than 120 °, and perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
2. flexible printed wiring board according to claim 1 is characterized in that: described electric insulation layer is made by polyimides.
3. flexible printed wiring board, it is characterized in that: comprise electric insulation layer, bond layer and conductor layer at least, wherein, 10 mean roughness on described electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and contact angle is more than or equal to 60 ° and less than 120 °, perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
4. flexible printed wiring board according to claim 3 is characterized in that: described electric insulation layer is made by polyimides.
5. according to each described flexible printed wiring board in the claim 1 to 4, it is characterized in that: conductor layer is provided with the cover layer that comprises bond layer and electric insulation layer, 10 mean roughness on the electric insulation layer surface in the described cover layer are more than or equal to 1.5 μ m and less than 2.0 μ m, and contact angle is more than or equal to 60 ° and less than 120 °, perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
6. multi-layer soft printing circuit board, it is characterized in that: lamination the described flexible printed wiring board of plural claim 5, be can be crooked state, and the electric insulation layer surface of the plural flexible printed wiring board that exposes is opposed mutually, be non-adhering state, the part of described flexible printed wiring board is laminated on respectively on first multi-layer soft printing circuit board and second multi-layer soft printing circuit board.
7. portable telephone terminal that adopts multi-layer soft printing circuit board, comprise the articulated section that rotatably connects first housing and second housing, it is characterized in that: by bend described articulated section, multi-layer soft printing circuit board according to claim 6, the electric insulation layer surface of the plural flexible printed wiring board that it exposes is opposite each other, is non-adhering state.
8. metal-coated laminated board, it is characterized in that: be used for each described flexible printed wiring board of claim 1 to 6 or the described portable telephone terminal of claim 7, at least comprise electric insulation layer, reach the conductor layer before circuit forms, wherein, 10 mean roughness on described electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and contact angle is more than or equal to 60 ° and less than 120 °, and perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
9. cover layer, it is characterized in that: be used for claim 5 or 6 described flexible printed wiring boards or the described portable telephone terminal of claim 7, comprise bond layer and electric insulation layer, wherein, 10 mean roughness on described electric insulation layer surface are more than or equal to 1.5 μ m and less than 2.0 μ m, and contact angle is more than or equal to 60 ° and less than 120 °, and perhaps, 10 mean roughness are more than or equal to 2.0 μ m and less than 4.0 μ m.
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| JP2005004383 | 2005-01-11 | ||
| JP2005-004383 | 2005-01-11 | ||
| JP2005004383A JP4162659B2 (en) | 2005-01-11 | 2005-01-11 | Flexible printed wiring board, multilayer flexible printed wiring board, and mobile phone terminal using the multilayer flexible printed wiring board |
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| CN1805652A true CN1805652A (en) | 2006-07-19 |
| CN1805652B CN1805652B (en) | 2012-04-25 |
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| Country | Link |
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| JP (1) | JP4162659B2 (en) |
| KR (1) | KR100750019B1 (en) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101501821B (en) * | 2006-08-07 | 2011-02-09 | 住友电气工业株式会社 | Method for manufacturing electronic circuit component |
| WO2012122685A1 (en) * | 2011-03-15 | 2012-09-20 | 珠海元盛电子科技股份有限公司 | Layered fpc for folding/sliding cover cell phone and manufacturing method as the same |
| CN104968253A (en) * | 2013-02-07 | 2015-10-07 | 奥林匹斯冬季和Ibe有限公司 | Hermetic feedthrough, method for producing a hermetic feedthrough, printed circuit board, and surgical instrument |
| CN105934347A (en) * | 2014-01-30 | 2016-09-07 | 惠普发展公司，有限责任合伙企业 | Printed circuit board fluid ejection apparatus |
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| ES2374181T3 (en) | 2006-07-19 | 2012-02-14 | B-Core Inc. | OPTICAL SYMBOL, ARTICLE TO WHICH THE OPTICAL SYMBOL IS SET, METHOD FOR SETTING AN OPTICAL SYMBOL TO AN ARTICLE, AND METHOD FOR THE RECOGNITION OF A CODE BY OPTICAL RECOGNITION. |
| JP4845705B2 (en) * | 2006-12-19 | 2011-12-28 | 日東電工株式会社 | Printed wiring board, manufacturing method thereof, and electronic device |
| TWI424802B (en) * | 2007-02-20 | 2014-01-21 | Hitachi Chemical Co Ltd | Flexible multilayer wiring board |
| JP2008282352A (en) | 2007-05-14 | 2008-11-20 | B-Core Inc | Marking method by shielding, marking method by deletion, and marking method by change of color |
| US8383230B2 (en) | 2007-05-24 | 2013-02-26 | Arisawa Mfg. Co., Ltd. | Flexible printed wiring board, multilayered flexible printed wiring board, and mobile telephone terminal employing multilayered flexible printed wiring board |
| CN101801156B (en) * | 2009-02-06 | 2013-02-27 | 周伯如 | Method for manufacturing flexible printed circuit board and structure thereof |
| CN102529271B (en) * | 2011-12-23 | 2014-12-24 | 云南云天化股份有限公司 | Polyimide thin film for flexible circuit board, and preparation method thereof |
| KR20140148111A (en) * | 2013-06-21 | 2014-12-31 | 삼성전기주식회사 | Rigid flexible printed circuit board and method for manufacturing thereof |
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| JPH07312469A (en) * | 1994-05-16 | 1995-11-28 | Nippon Mektron Ltd | Structure of bent part of multilayer flexible circuit board |
| JP2002261450A (en) | 2001-02-28 | 2002-09-13 | Shin Etsu Chem Co Ltd | Multilayer flexible printed wiring board |
| KR100828520B1 (en) * | 2001-11-23 | 2008-05-13 | 삼성전자주식회사 | Liquid crystal display module |
| KR101018944B1 (en) | 2003-03-04 | 2011-03-02 | 니폰 제온 가부시키가이샤 | Process for producing multilayer printed wiring board and multilayer printed wiring board |
| KR100477378B1 (en) * | 2003-03-21 | 2005-03-18 | 주식회사 에스아이 플렉스 | Manufacturing method for Multi-layer Flexible Printed Circuit Board |
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2005
- 2005-01-11 JP JP2005004383A patent/JP4162659B2/en active Active
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101501821B (en) * | 2006-08-07 | 2011-02-09 | 住友电气工业株式会社 | Method for manufacturing electronic circuit component |
| US8026185B2 (en) | 2006-08-07 | 2011-09-27 | Sumitomo Electric Industries, Ltd. | Method for manufacturing electronic circuit component |
| WO2012122685A1 (en) * | 2011-03-15 | 2012-09-20 | 珠海元盛电子科技股份有限公司 | Layered fpc for folding/sliding cover cell phone and manufacturing method as the same |
| CN104968253A (en) * | 2013-02-07 | 2015-10-07 | 奥林匹斯冬季和Ibe有限公司 | Hermetic feedthrough, method for producing a hermetic feedthrough, printed circuit board, and surgical instrument |
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| US9962936B2 (en) | 2014-01-30 | 2018-05-08 | Hewlett-Packard Development Company, L.P. | Printed circuit board fluid ejection apparatus |
| CN105934347B (en) * | 2014-01-30 | 2019-04-02 | 惠普发展公司，有限责任合伙企业 | Printed wiring board fluid ejection apparatus |
| US10500858B2 (en) | 2014-01-30 | 2019-12-10 | Hewlett-Packard Development Company, L.P. | Printed circuit board fluid ejection apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1805652B (en) | 2012-04-25 |
| TW200638813A (en) | 2006-11-01 |
| JP4162659B2 (en) | 2008-10-08 |
| JP2006196548A (en) | 2006-07-27 |
| TWI306726B (en) | 2009-02-21 |
| KR100750019B1 (en) | 2007-08-16 |
| KR20060082043A (en) | 2006-07-14 |
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