CN101547559A - Flexible copper clad laminate - Google Patents
Flexible copper clad laminate Download PDFInfo
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- CN101547559A CN101547559A CN200910129448A CN200910129448A CN101547559A CN 101547559 A CN101547559 A CN 101547559A CN 200910129448 A CN200910129448 A CN 200910129448A CN 200910129448 A CN200910129448 A CN 200910129448A CN 101547559 A CN101547559 A CN 101547559A
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- copper foil
- layer
- polyimide resin
- clad laminate
- resin layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
The present invention provides a flexible copper clad laminate, which excellent thermal stability and size stability etc., capable satisfying requirement of high-integration and high-intensity, and capable of improving bonding reliability between a copper foil and a polyimide resin layer, and restraining circuit removal in chemical grinding. In the copper clad laminate with copper foil on single side or both sides of the polyimide resin layer, the copper foil contacts with a surface treating layer formed with a plurality of treating layers containing silane coupling treating layer on copper foil layer of the polyimide resin layer, the surface treating layer contains copper, cobalt, nickel and zinc, and ratio of the nickel/(nickel+cobalt+zinc) is higher than 0.23 (measured by ICP-AES), content of zinc is 0.2 to 0.6 mg/dm2, the silane coupling treating layer is formed with silane coupling agent having amidogen.
Description
Technical field
The present invention relates to insulating barrier of forming by polyimide resin and the flexible copper clad laminate that is provided with Copper Foil at its single or double.
Background technology
In recent years, along with multifunction, miniaturization and the lighting of other various electronic installations such as mobile phone or digital camera, digital code camera, PDA, vehicle navigation device, hard disk, the example that adopts the high and flexible printing substrate easily slimming of the circuit degree of freedom to replace so far the rigid substrates that uses with baseplate material as this electron-like circuit increases.And, about the employed flexible printing substrate of this class device of High Level more gradually, just increasing the demand of more small-sized densification, multiple stratification, tinyization, high-fire resistance etc.
In order to satisfy such requirement, in the special fair 6-93537 communique of patent documentation 1 Japan etc., disclose a kind of on conductor, directly the coating and formed polyimide resin layer, and carry out multiple stratification and form with the different a plurality of polyimide resin layers of thermal coefficient of expansion, dimensional stability, bonding force for variations in temperature are provided thus, and the good flexible printing substrate of the reliabilities such as flatness after the etching.
In such copper clad laminate that does not have employed adhesive phase in the flexible printing substrate (for example in patent documentation 2 Japanese kokai publication hei 2-292894 communiques, patent documentation 3 Japanese kokai publication hei 6-169168 communiques, patent documentation 4 Japanese kokai publication hei 8-335775 communiques etc.), in order to improve the bonding force with resin bed, use the Copper Foil of copper foil surface through roughened.
Yet, in recent years, when carrying out the becoming more meticulous of circuit, on circuit end after the circuit fabrication and polyimides, be prone to residue, thereby be necessary to remove residue.In addition, on pre-treatment step, need the cleaning circuit surface as the copper foil surface in plating step of circuit fabrication etc.For this reason, except the acid of carrying out copper foil surface is cleaned, also by grind the step of copper foil surface as the chemical grinding liquid of principal component with the soup of dissolved coppers such as hydrogen peroxide/sulfuric acid.Yet, because in the made copper clad laminate of the Copper Foil stated in the use through roughened, particularly after this copper clad laminate is carried out circuit fabrication in the flexible printing substrate of gained, if carry out such chemical grinding, then chemical grinding liquid can infiltrate the marginal portion of circuit, thereby easily causes the peel strength of circuit to reduce, and if carry out becoming more meticulous of circuit-line, then can peel off and cause circuit to float and cause broken string, thereby must improve because of circuit.
Summary of the invention
The invention provides the requirement that a kind of thermal endurance and dimensional stability etc. are good, can satisfy booming in recent years highly integrated and densification in the field of e-machine class, and the method peeled off of the circuit when improving adhesion reliability between Copper Foil and polyimide resin layer and suppress chemical grinding.
In order to solve the problems of the technologies described above, the back is found after deliberation, and the surface characteristic of the Copper Foil that will contact with polyimide resin layer is controlled at particular range, can improve the adhesion reliability between Copper Foil and polyimide resin layer, thereby finishes the present invention.
In other words, the invention provides a kind of flexible copper clad laminate, it is for there being the copper clad laminate of Copper Foil at the single or double lamination of polyimide resin layer, it is characterized in that, wherein, the copper foil surface that contacts with polyimide resin layer of described Copper Foil has the surface-treated layer of being made up of a plurality of processing layers that comprise silane coupled processing layer, this surface-treated layer contains copper, cobalt, nickel and zinc, the ratio of nickel/(nickel+cobalt+zinc) is (according to ICP-AES (Inductively Coupled Plasma-Atomic EmissionSpectroscopy more than 0.23, induction coupling electricity slurry-atom luminescent spectrum method) mensuration obtains), and zinc content is 0.2 to 0.6mg/dm
2, described silane coupled processing layer forms by having amino silane coupler.
It below is the preferred form of flexible copper clad laminate of the present invention.
1) the silane coupled processing layer in the surface-treated layer is positioned at outermost layer.
2) above-mentioned polyimide resin layer is made up of multilayer, and the polyimide resin layer that contacts with Copper Foil (A) is made up of thermoplastic polyimide resin.
3) Copper Foil is rolling Copper Foil (also claiming rolled copper foil), and the surface roughness of the surface treated copper foil surface that contacts with polyimide resin layer (Rz) is 0.5 to 2 μ m.
4) the initial stage bonding force of the 1mm width of polyimide resin layer and Copper Foil is more than the 0.6kN/m.
Copper clad laminate of the present invention has good resin bed and the bonding strength between Copper Foil, thermal endurance, anti-flammability and dimensional stability etc., and the fine circuitry excellent processability, and can not take place because of bad situations such as peeling off of causing of chemical grinding.Therefore, when being used in electrical equipment, electronic component, applicable to the purposes that requires good reliability, particularly fine-line as the flexible printing substrate.
Embodiment
Below describe the present invention in detail.
Flexible copper clad laminate of the present invention is made up of with Copper Foil the polyimide resin layer (being also referred to as insulating barrier) as insulating barrier.Copper Foil can use the Copper Foil that for example obtains according to existing manufacture methods such as rolling Copper Foil, electrolytic copper foils.The preferred thickness of Copper Foil is 6 to 35 μ m, more preferably 9 to 18 μ m.If the thickness of Copper Foil does not reach 6 μ m, then as the manufacturing step of a large amount of production lines when producing copper clad laminate in, the situation of tension force etc. may appear being difficult to adjusting, if but surpass 35 μ m, then the bendability of copper clad laminate is relatively poor.
In order to improve and as the bonding force between the polyimide resin layer of insulating barrier, employed Copper Foil is to have the surface-treated layer of being made up of a plurality of processing layers that comprise silane coupled processing layer.Except silane coupled processing layer, processing layer preferably comprises the roughened layer.
Degree preferred surface roughness (Rz) in order to the roughened that forms the roughened layer is 0.5 to 2 μ m, more preferably 0.5 to 1 μ m.Surface roughness in the literary composition (Rz) is meant defined 10 mean roughness by JIS B0601 (1994).This roughened is to make metallic (roughening particle) be attached to copper foil surface to wait and improve surface roughness.Thus, between insulating barrier and Copper Foil, can produce and decide anchor effect (anchor effect) and improve bonding force.If above-mentioned surface roughness (Rz) do not reach 0.5 μ m, then can't expect to insulating barrier decide the anchor effect, and bonding force reduces.In addition,, then do not remove during the etching of roughening particle in circuit fabrication, thereby may have the situation that is present in as etch residues on circuit end or the insulating barrier if surface roughness (Rz) surpasses 2 μ m.And this etch residues may cause the so-called short circuit between circuit or the bad situations such as copper stripping of migration (migration) when retrofit.
Employed roughening particle can use copper separately in this roughened, or uses copper+nickel or copper+cobalt+alloys such as nickel.In addition, after being adhered to, also can further handle on the roughening particle by copper, nickel or nickel+cobalt.But,, can not peel off whole copper, nickel, the cobalt of being necessary for of this roughened layer because of chemical grinding because circuit fabrication is good.When in roughened, only using copper, then easily oxidation and easily cause variable color etc.In addition, if use copper and nickel or only use nickel, though then strengthen for the patience of chemical grinding, employed copper electroplating liquid when not being soluble in circuit fabrication, and the situation of etch residues may take place easily to produce.If use copper and cobalt or only use cobalt, then acid resistance worsens, and peels off thereby might circuit take place when chemical grinding.
Employed in the present invention Copper Foil (is preferably in above-mentioned roughened layer or on the roughened layer) zinc that contains in surface-treated layer be 0.2 to 0.6mg/dm
2When the layer that will contain zinc is arranged on the roughened layer, can handle and cambium layer by separating out.In the present invention, both can suppress the copper oxidation, and can suppress again to peel off because of the circuit that chemical grinding causes by this zinc processing.If the content of zinc does not reach 0.2mg/dm
2, the circuit variable color or the oxidation that then take place to cause because of oxidation cause the Copper Foil embrittlement, thereby easily cause the circuit broken string.In addition, if the content of zinc surpasses 0.6mg/dm
2, then zinc itself is not acidproof, thus the circuit that the Yi Fashengyin chemical grinding causes peel off, and easily break.Simultaneously, separate out processing, so long as the means that can above-mentioned metal be separated out with scheduled volume as metallide etc. then are not particularly limited for above-mentioned.
For the bonding force of further raising with insulating barrier, employed in the present invention Copper Foil is to have by having the amino formed silane coupled processing layer of silane coupler.This silane coupled processing layer preferably is present in the outermost layer of surface-treated layer.Example with amino silane coupler is as N-2-(amino-ethyl) gamma-amino propyl trimethoxy silicane, N-3-(4-(the amino propoxyl group of 3-) butoxy) propyl group-3-TSL 8330, N-phenyl-3-aminopropyl trimethoxysilane etc.This one type of silane coupling agent can use separately, or is used in combination, and when use is multiple, has amino silane coupler more than a kind as long as contain.In addition, before carrying out silane coupled processing, for realize better and insulating barrier between the purpose of bonding force, also can carry out chromate and handle.
The example of silane coupled processing method as: when using above-mentioned coupling agent, at first, in water, make the coupling agent dissolving of scheduled volume as solvent after, coat on the copper foil surface after above-mentioned metal is separated out processing and make its dry method.At this moment, as required, also can carry out heat treated.In addition, be coated with the method for coupling agent soluble in water, for example can use: existing methods such as infusion process, spray process, spray-on process for copper foil surface.
Through above-mentioned processing, the surface-treated layer of whole copper foil contains copper, cobalt, nickel and zinc.And must make the ratio of nickel/(nickel+cobalt+zinc) is more than 0.23, and is preferably 0.24 to 0.3.If the ratio of nickel/(nickel+cobalt+zinc) does not reach 0.23, then in the circuit end circuit takes place easily and peel off when chemical grinding.At this, the mensuration of copper, cobalt, nickel and zinc is measured according to ICP-AES and is obtained, and measures according to the condition of record in an embodiment.
Lamination is as the polyimide resin layer of insulating barrier on being provided with as the face of the surface-treated layer side of the Copper Foil of above-mentioned surface-treated layer.The polyimide resin that constitutes this polyimide resin layer can use equimolar in fact two amine components and acid dianhydride composition generally by following formula (1) expression, and according to the existing method manufacturing of in organic polar solvent, carrying out polymerization.
In general formula (1), Ar
1For having 4 valency organic groups of 1 above aromatic ring, Ar
2For having the divalent organic group of 1 above aromatic ring.And, Ar
1Be the residue of acid dianhydride, Ar
2Residue for diamines.
The example of acid dianhydride as: by O (CO)
2-Ar
1-(CO)
2The aromatic acid dianhydride that O is represented.Preferred Ar
1Example be 4 valency organic groups shown below.
Acid dianhydride can be used alone or mixed use of two or more.Wherein acid dianhydride is preferably selected from pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride (BTDA), 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydride (DSDA), 4,4 '-oxygen two phthalandione dianhydrides (ODPA).
The example of diamines as: by H
2N-Ar
2-NH
2Represented aromatic diamine.Preferred Ar
2Example divalent organic group as shown below.
In these diamines, preferred example is as diamino-diphenyl ether (DAPE), 2,2 '-dimethyl-4,4 '-benzidine (hereinafter referred to as m-TB), p-phenylenediamine (PPD) (p-PDA), 1, two (4-amino-benzene oxygen) benzene (TPE-R), 1 of 3-, two (3-amino-benzene oxygen) benzene (APB), 1 of 3-, two (4-amino-benzene oxygen) benzene (TPE-Q), 2 of 4-, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-.
The example of the solvent that uses during polymerization is as dimethylacetylamide, n-methylpyrrole pyridine ketone, 2-butanone, diethylene glycol dimethyl ether, dimethylbenzene etc., and they can use separately or more than 2 kinds and use.In addition, the resin viscosity of the polyamic acid of polymerization gained (polyimides predecessor) is preferably 500cps to 35000cps.
The polyimide resin layer of flexible copper clad laminate of the present invention can be formed or be made up of multilayer by individual layer.For the dimensional stability that makes flexible copper clad laminate and preferable with the bonding strength of Copper Foil, preferred multilayer.When polyimide resin layer is multilayer, be 30 * 10 preferably with coefficient of linear expansion (CTE)
-6(be preferably 1 to 30 * 10 (1/K)
-6The resin bed of low linear expansion coefficient scope (1/K)) is provided with the thermoplastic polyimide resin layer as main polyimide resin layer (B) on its single or double.Preferably with the polyimide resin layer (A) that contacts a side with Copper Foil as the thermoplastic polyimide resin layer.
The thermoplastic polyimide resin layer is meant that coefficient of linear expansion (CTE) surpasses 30 * 10 in the literary composition
-6(1/K), and glass transition temperature be below 330 ℃.Preferred thermoplastic polyimide resin series of strata coefficient of linear expansion is 30 * 10
-6To 60 * 10
-6(1/K), and glass transition temperature be 200 to 330 ℃.If the CTE of main polyimide resin layer (B) is greater than 30 * 10
-6/ ℃, be prone to the situation that warpage is aggravated when then forming copper clad laminate.In addition, because dimensional stability reduces, therefore be not suitable as goods.The thickness of main polyimide resin layer (B) is preferably more than 50% of full polyimide resin layer thickness, and more preferably 70 to 95%.
Be not particularly limited for the method that forms polyimide resin layer, preference will be as will directly coating surface treated copper foil surface as the resin solution of the polyamic acid of the predecessor of polyimide resin, and the temperature below 150 ℃ in resin solution contained removal of solvents to a certain degree after, carry out heat treatment about 5 to 40 minutes in the temperature range of 100 to 450 ℃ (being preferably 250 to 450 ℃) again, thereby carry out the drying and the imidizate of solvent.When polyimide resin layer being arranged to more than 2 layers, preferably after with the coating of the resin solution of first polyamic acid, drying, resin solution coating, drying with second polyamic acid, below carry out equally, successively with after the resin solution coating of the 3rd later polyamic acid, the drying, carry out heat treatment about 5 to 40 minutes together 250 to 450 ℃ temperature ranges, thereby carry out imidizate.If heat treated temperature is lower than 100 ℃, then the reaction of the dehydration closed-loop of polyimides can't fully be carried out, but if surpass 450 ℃, polyimide resin layer and the Copper Foil situation because of deteriorations such as oxidations takes place easily then.
Preferred 6 to the 45 μ m of the thickness of polyimide resin layer, more preferably 9 to 40 μ m.If the thickness of insulating barrier does not reach 6 μ m, then when making copper clad laminate etc., in carrying, be prone to the bad situation of fold generation etc., but if surpass 45 μ m, then when making copper clad laminate easily in aspect generation problems such as dimensional stability or bendabilities.
Flexible copper clad laminate of the present invention can be the single face copper clad laminate that only has Copper Foil in single face one side of polyimide resin layer, also can be the two-sided double-sided copper-clad laminated sheet that all has Copper Foil at polyimide resin layer.In addition, in order to obtain the double-sided copper-clad laminated sheet, can be after forming the single face copper clad laminate, by making polyimide resin layer face-to-face and give pressing by hot pressing and form, or Copper Foil is pressed on the polyimide resin layer of single face copper clad laminate and formation etc. and obtaining.
Flexible copper clad laminate of the present invention is preferably more than the 0.6kN/m at the initial stage bonding force of the 1mm of polyimide resin layer and Copper Foil width, more preferably 0.8 to 2.0kN/m.This initial stage bonding force is the value that records with the condition of putting down in writing in an embodiment.In order to obtain this initial stage bonding force, except with the polyimide resin layer that contacts with Copper Foil as the thermoplastic polyimide resin layer, can reach in above-mentioned scope by the amount of the special metal in the surface-treated layer that makes Copper Foil.
Embodiment
Below, be described in more detail the present invention according to embodiment.In addition, in following embodiment, as long as do not specify that various assessments are according to following method and record.
The mensuration of bonding force
Bonding force between Copper Foil and the polyimide resin layer, be the flexible copper clad laminate that obtains on Copper Foil, forming the insulating barrier of forming by polyimide resin, carry out circuit fabrication and become live width 1mm, use Japan smart machine limited company system stretching testing machine (Strograph M1), Copper Foil is peeled and records towards 180 ℃ of directions.
The mensuration of the amount of metal of surface-treated layer
The mensuration of the amount of metal of the surface metal-layer of Copper Foil is undertaken by ICP-AES (PerkinElmer corporate system Optima 4300DV).Mensuration be with Copper Foil with surface-treated layer as sample, after the 2g sample is carried out resolution process with nitric acid and hydrochloric acid, capacity is fixed in 100mL, carry out after diluting 10 times.
The mensuration of chemical grinding patience
The mensuration of chemical grinding patience, be for flexible copper clad laminate, carry out circuit fabrication and become live width 1mm, and in 40 ℃ of chemical grinding liquid that impregnated in 2.5 weight % hydrogen peroxide/10 weight % sulfuric acid, after 2 minutes, use 200 times light microscope to confirm that from the insulating barrier side circuit end has or not variable color.
Synthesis example 1
Be equipped with thermocouple and mixer and can importing the N that packs in the reaction vessel of nitrogen, N-dimethylacetylamide.In this reaction vessel, make 2,2 while stirring '-dimethyl-4,4 '-benzidine (m-TB) dissolves in container.Then, adding 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and pyromellitic acid anhydride (PMDA).The mode that adds is to make that the adding total amount of monomer is 15 weight %, and the molar ratio of each acid anhydrides (BPDA:PMDA) is 20:80.Continue stirring 3 hours afterwards, thereby obtain the resin solution a of polyamic acid.The solution viscosity of the resin solution a of polyamic acid is 20000cps.Polyimides by this polyamic acid gained shows 25 * 10
-6(1/K) Yi Xia low linear expansion coefficient, thus the character of non-thermal plasticity had.
Synthesis example 2
Be equipped with thermocouple and mixer and can importing the N that packs in the reaction vessel of nitrogen, N-dimethylacetylamide.Make 2 while stirring in this reaction vessel, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-dissolve in container.Then, add pyromellitic acid anhydride, the adding total amount that makes monomer is 12 weight %.Afterwards, continue stirring 3 hours, thereby obtain the resin solution b of polyamic acid.The solution viscosity of the resin solution b of polyamic acid is 3000cps.Polyimides by this polyamic acid gained shows above 30 * 10
-6Coefficient of linear expansion (1/K), thus thermoplastic character had.
Embodiment 1
The rolling Copper Foil that preparation has the amino silane coupled processing of silane coupler as the process of surface-treated layer and contains the metallic element shown in the table 1 is as Copper Foil.The thickness of this Copper Foil is 18 μ m, and surface roughness (Rz) is 0.8 μ m.On this Copper Foil, be coated with the resin solution a of the polyamic acid that is modulated in the resin solution b of the polyamic acid that is modulated in the synthesis example 2 and the synthesis example 1 and dry successively, heat-treating about 10 minutes more than 300 ℃ at last, thereby the thickness that obtains polyimide resin layer is the flexible single-side copper clad laminate of 25 μ m.Simultaneously, in polyimide resin layer, be 23 μ m by the layer of the resin solution a gained of polyamic acid, be 2 μ m by the layer of the resin solution b gained of polyamic acid.The initial stage bonding force that the 1mm of this copper clad laminate peels off is 1.0kN/m.In addition, after this sample is carried out chemical grinding, can't confirm to have variable color in the circuit end.The result is as shown in table 2.
Embodiment 2, comparative example 1,2
Except using the different rolling Copper Foil of surface metal amount as shown in table 1, adopt similarly to Example 1 method assessment peel strength, chemical grinding patience.The result is as shown in table 2.
In table 1, Ni is than being nickel amount/(nickel amount+cobalt amount+zinc amount).
Table 1
Table 2
| Peel strength | State after chemical grinding is handled | |
| Embodiment 1 | 1.0kN/m | No variable color |
| Embodiment 2 | 1.0 | No variable color |
| Comparative example 1 | 1.0 | All have in the entire circuit end because of circuit and peel off the variable color that causes |
| Comparative example 2 | 1.0 | All have in the entire circuit end because of circuit and peel off the variable color that causes |
The copper clad laminate of gained is handled the back at chemical grinding and has not been observed variable color in the circuit end among the embodiment 1,2, thereby confirms that circuit does not take place to be peeled off.On the other hand, 1,2 affirmations of comparative example all have in the entire circuit end because of circuit and peel off the variable color that causes.
Therefore, the flexible copper clad laminate of gained of the present invention is not peeled off owing to can not produce circuit behind chemical grinding, thus the reliability height, and confirm as the material that is suitable for the retrofit purposes.
Claims (5)
1, a kind of flexible copper clad laminate, its single or double lamination at polyimide resin layer has Copper Foil, it is characterized in that, the copper foil surface of described Copper Foil contact polyimide resin layer has the surface-treated layer of being made up of a plurality of processing layers that comprise silane coupled processing layer, this surface-treated layer contains copper, cobalt, nickel and zinc, the ratio of nickel/(nickel+cobalt+zinc) that records according to ICP-AES is more than 0.23, and zinc content is 0.2 to 0.6mg/dm
2, described silane coupled processing layer forms by having amino silane coupler.
2, flexible copper clad laminate according to claim 1, wherein, the silane coupled processing layer in the described surface-treated layer is positioned at outermost layer.
3, flexible copper clad laminate according to claim 1 and 2, wherein, polyimide resin layer is made up of multilayer, and the polyimide resin layer that contacts with Copper Foil (A) is made up of thermoplastic polyimide resin.
4, according to each described flexible copper clad laminate in the claim 1 to 3, wherein, Copper Foil is the rolling Copper Foil, and the surface roughness of the surface treated copper foil surface that contacts with polyimide resin layer (Rz) is 0.5 to 2 μ m.
5, according to each described flexible copper clad laminate in the claim 1 to 4, wherein, the initial stage bonding force of the 1mm width of polyimide resin layer and Copper Foil is more than the 0.6kN/m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008078060A JP4907580B2 (en) | 2008-03-25 | 2008-03-25 | Flexible copper clad laminate |
| JP2008-078060 | 2008-03-25 | ||
| JP2008078060 | 2008-03-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101547559A true CN101547559A (en) | 2009-09-30 |
| CN101547559B CN101547559B (en) | 2012-08-22 |
Family
ID=41194339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101294482A Active CN101547559B (en) | 2008-03-25 | 2009-03-20 | Flexible copper clad laminate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4907580B2 (en) |
| KR (1) | KR101574587B1 (en) |
| CN (1) | CN101547559B (en) |
| TW (1) | TWI519412B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102783255A (en) * | 2010-02-24 | 2012-11-14 | 吉坤日矿日石金属株式会社 | Copper foil for printed circuit board and copper-clad laminate for printed circuit board |
| CN103732798A (en) * | 2011-06-14 | 2014-04-16 | 大日本印刷株式会社 | Conductive base for forming wiring pattern of collector sheet for solar cells, and method for producing collector sheet for solar cells |
| CN105323958A (en) * | 2014-05-28 | 2016-02-10 | Jx日矿日石金属株式会社 | Surface-processed copper foil, copper foil with carrier, laminated body, printed circuit board, electronic equipment, manufacturing method for surface-processed copper foil and manufacturing method for printed circuit board |
| CN106028633A (en) * | 2015-03-31 | 2016-10-12 | 新日铁住金化学株式会社 | Copper-clad laminate and printed wiring board |
| CN106795644A (en) * | 2014-09-09 | 2017-05-31 | 古河电气工业株式会社 | Copper foil for printed wiring board and copper clad laminate |
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- 2009-03-16 TW TW098108377A patent/TWI519412B/en active
- 2009-03-20 CN CN2009101294482A patent/CN101547559B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4907580B2 (en) | 2012-03-28 |
| CN101547559B (en) | 2012-08-22 |
| KR20090102633A (en) | 2009-09-30 |
| JP2009226874A (en) | 2009-10-08 |
| TW200940328A (en) | 2009-10-01 |
| TWI519412B (en) | 2016-02-01 |
| KR101574587B1 (en) | 2015-12-04 |
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