CN102740613B - Metal-clad - Google Patents
Metal-clad Download PDFInfo
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- CN102740613B CN102740613B CN201210093700.0A CN201210093700A CN102740613B CN 102740613 B CN102740613 B CN 102740613B CN 201210093700 A CN201210093700 A CN 201210093700A CN 102740613 B CN102740613 B CN 102740613B
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- shape
- lugs
- metal
- polyimide layer
- ratio
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Classifications
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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
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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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
- H05K1/03—Use of materials for the substrate
-
- 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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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The present invention provides a kind of metal-clad, and it is on the basis of dimensional stability, and excellent heat resistance, the bonding reliability especially inhibiting micropore that the interlayer at heating pressure side produces are the most excellent.For this plywood, the glass transition temperature of the polyimide layer i connected with metal forming is more than 300 DEG C and is set in the roughening treatment face of metal forming: (a) surface roughness Rz is 0.5～4 μm；B the skin section in () roughening treatment face forms multiple micro crowning shape, length-width ratio H/L represented with the ratio of the rising height H and root width L of wherein 1 thrust 1.5～5 scope, its rising height in the ratio of the shape for lugs of the scope of 1～3 μm relative to the quantity of whole shape for lugs for less than 50%；C between () thrust, the degree of depth is more than 0.5 μm and the abutment lug thing spacing existence ratio in the gap of the scope of 0.001～1 μm is less than the 50% of whole shape for lugs number.
Description
Technical field
The present invention relates to be suitable for being used in the metal-clad of flexible circuit board, particularly relate to insulating barrier by polyamides Asia
What polyimide resin was formed has the flexible metal-coated lamination of flexibility.
Background technology
In recent years, along with mobile phone, digital camera, DV, PDA, automobile navigation instrument, hard disk, other various electricity
The high performance of subset, miniaturization and lightweight, as their electric distribution baseplate material, replace making in the past always
Rigid substrates and use the example of the flexible printed board that the degree of freedom of distribution is high, be prone to slimming to be gradually increased.Further,
For to higher degreeization development, for the flexible printed board of these equipment for, more Miniature high-density, multilamellar
Change, become more meticulous, high resistance to transconversion into heat etc. requires to step up.
In response to these requirements, patent documentation 1 grade discloses on conductor, is directly coated with formation polyimide resin
Layer and carry out multiple stratification and form multiple polyimide resin layers that thermal coefficient of expansion is different, thus provide variations in temperature
The method of the aspect such as dimensional stability, bonding force and flatness after the etching flexible printed board of excellent in reliability.
For the copper-clad laminated board without bond layer used in such flexible printed board, such as, such as patent
Document 2, patent documentation 3, patent documentation 4 etc. record as, in order to improve with the bonding force of resin bed and use copper foil surface
The Copper Foil of roughening treatment.
But, in recent years, in order to tackle the rising along with unleaded solder joints temperature, as patent documentation 5 is recorded
As, at Copper Foil and polyimide layer when thus there is thermo-compressed in the high resistance to transconversion into heat of the polyimide resin layer that connects with Copper Foil
Between the infiltration of sour cleanout fluid when easily generating micropore, circuit fabrication cause occurring the bonding reliabilities such as distribution peeling to reduce
Problem.For this problem, as patent documentation 6 is recorded, there is suppression roughening treatment height, control roughening of copper foil process face
The method of coating layer, but according to the method, possible initial stage peel strength can reduce, unresolved technical problem.
Patent documentation 1: Japanese Patent Publication 6-93537 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2-292894 publication
Patent documentation 3: Japanese Unexamined Patent Publication 6-169168 publication
Patent documentation 4: Japanese Unexamined Patent Publication 8-335775 publication
Patent documentation 5:WO2002/085616
Patent documentation 6:WO2010/010892
Summary of the invention
It is an object of the invention to provide a kind of metal-clad, for this metal-clad, although be roughened
The polyimide layer that the metal forming processed connects has high-fire resistance, but inhibits and generate between metal forming and polyimide layer
Micropore and inhibit by improving metal level and the bonding reliability of polyimide layer because the infiltration of sour cleanout fluid causes
Circuit peel off.
The present inventor etc. conduct in-depth research to solve above-mentioned problem, found that by using metal foil surface
Roughening character is the metal-clad of characteristic trait, and the resin with particular characteristics is used for the polyamides connected with this metal forming
Imide resin such that it is able to solve above-mentioned technical problem, until completing the present invention.
That is, the present invention relates to a kind of metal-clad, it is characterised in that the one or two sides at polyimide layer has
Metal forming, the glass transition temperature of the polyimide layer (i) connected with above-mentioned metal forming is more than 300 DEG C, above-mentioned metal forming
The roughening treatment face connected with polyimide layer meet following condition (a)～(c).
A the surface roughness (Rz) in () roughening treatment face is in the scope of 0.5～4 μm
B the skin section in () roughening treatment face is the micro crowning shape formed by multiple roughening particles, with above-mentioned fine prominent
The length-width ratio (H/L) that the ratio of rising height H and root width L of 1 thrust playing shape represents 1.5～5 scope and
Rising height is less than 50% in the ratio of the shape for lugs of the scope of 1～3 μm relative to the quantity of whole shape for lugs
C () degree of depth between adjacent thrust is that more than 0.5 μm and abutment lug thing spacing are in 0.001～1 μm
The existence ratio in the gap of scope is less than the 50% of whole shape for lugs number
The metal-clad of the present invention, the polyimides not merely comprising insulating barrier has thermostability, the chi of display excellence
Very little stability, can also suppress between metal forming and the polyimide layer connected with it produce micropore, the electricity of flexible wiring sheet
The chemical reagent resistance that road adds man-hour etc. is the most excellent, thus be applicable to requirement fine processing circuit substrate, its serviceability non-
Chang Gao.
Accompanying drawing explanation
Fig. 1 is the ideograph of the roughening shape in the Copper Foil cross section for Copper Foil is described.
Fig. 2 is the Copper Foil cross-section photograph of the Copper Foil used in embodiment 1.
Fig. 3 is the Copper Foil cross-section photograph of the Copper Foil used in comparative example 2.
Symbol description
The width of the root of L micro crowning shape
The height of H micro crowning shape
1 thrust that p Yu q is adjacent
1 thrust that q Yu p is adjacent
Detailed description of the invention
The present invention described further below.
The metal-clad of the present invention has metal forming in the one or two sides of polyimides.For polyimide layer
Speech, as long as the glass transition temperature of the polyimide layer connected with metal forming is more than 300 DEG C, then can be that monolayer can also
Formed by multiple layers, but preferably by the polyimide layer (i) that glass transition temperature is more than 300 DEG C and other polyimides
Layer is formed, and other polyimide layer is by the glass with higher than the glass transition temperature of polyimide layer (i) more than 50 DEG C
The polyimide resin layer (ii) changing transition temperature is formed.As metal forming, as long as show aftermentioned surface coarsening shape, its kind
Class is just not particularly limited, but preferably Copper Foil or alloy Copper Foil.
As metal forming, when using Copper Foil, alloy Copper Foil, preferably their thickness is in the scope of 5～50 μm, if it is considered that
The suitability to flexible wiring substrate, the most more preferably in the scope of 9～30 μm.
The roughening treatment face connected with polyimide layer of the metal forming used in the present invention must is fulfilled for following condition (a)
～(c).
A the surface roughness (Rz) in () roughening treatment face is in the scope of 0.5～4 μm
B the skin section in () roughening treatment face is the micro crowning shape formed by multiple roughening particles, with above-mentioned fine prominent
The length-width ratio (H/L) that the ratio of rising height H and root width L of 1 thrust playing shape represents 1.5～5 scope and
Rising height is less than 50% in the ratio of the shape for lugs of the scope of 1～3 μm relative to the quantity of whole shape for lugs
C () degree of depth between adjacent thrust is that more than 0.5 μm and abutment lug thing spacing are in 0.001～1 μm
The existence ratio in the gap of scope is less than the 50% of whole shape for lugs number
First of all, it is necessary to the surface roughness in the roughening treatment face of making (Rz) is in the scope of 0.5～4 μm.If the value of Rz is not enough
0.5 μm, then metal forming reduces with the bonding force of polyimide layer；If it exceeds 4 μm, then erosion when circuit fabrication is become fine pattern
Quarter, residue increased, and its result electricity reliability reduces.Herein, the surface roughness (Rz) in roughening treatment face refers at JISB 0601-
The Rz of the definition regulation of " 5.1 ten mean roughness " of 1994 " being shown as the definition of surface roughness ".
Then, it is necessary to the skin section making roughening treatment face is the micro crowning shape formed by many roughening particles, above
The length-width ratio (H/L) that the ratio of the rising height H and root width L that state 1 thrust of micro crowning shape represents is 1.5～5
Scope and rising height be 50% in the ratio of the shape for lugs of the scope of 1～3 μm relative to the quantity of whole shape for lugs
Below.If the condition of above-mentioned length-width ratio and rising height is more than 50%, then roughening due to surface coarsening shape, so to resistance to
When the polyimide layer that hot (glass transition temperature) is high carries out adding thermo-compressed, illiquidity, easily generate micropore.
And then, for the roughening treatment face of metal foil surface, between adjacent thrust, the degree of depth is more than 0.5 μm, neighbour
Connect the thrust spacing existence ratio in the gap of the scope of 0.001～1 μm be necessary for the 50% of whole shape for lugs number with
Under.If this ratio is more than 50%, then can not be sufficiently carried out the resin filling to gap, easily generate micropore.
Herein, for the roughening treatment of the metal forming that the present invention uses, Fig. 1 is utilized to illustrate.Fig. 1 is metal forming to be cut
The surface portion in face is amplified and the figure of medelling ground expression.In the present invention, the most as shown in Figure 1, roughening treatment face is fine prominent
Playing the length-width ratio of shape, to be the height H with 1 thrust of micro crowning shape obtain divided by the root width L of thrust
Value.Rising height refers to represent the value of the length the longest apart from the center connecting adjacent valley portions.
It addition, for the above-mentioned condition (c) of the present invention, have between adjacent thrust the degree of depth be 0.5 μm with
On gap, judge with the existence ratio in the gap that the spacing of abutment lug thing in this gap is 0.001～1 μm.Fig. 1
In, thrust p and thrust q is adjacent thrust, has the gap of the 0.5 above degree of depth of μm between thrust p and q.And
And, this adjacent spacing is in the scope of 0.001～1 μm.In the present invention, such gap is the most less, if condition (c) changed
Sentence is talked about, then as the gap that the degree of depth between thrust is the 0.5 above degree of depth of μm and the adjacent spacing till this degree of depth
It is the quantity of less than 50% in the gap of scope of 0.001～1 μm relative to whole shape for lugs numbers.
The roughening shape that the metal foil surface used in the present invention is formed is preferably directed towards zenith directions and exists wider than root
The ratio of the shape for lugs of the degree big width of L is less than 20% relative to the quantity of whole shape for lugs, more preferably 10% with
Under.When this ratio is more than 20%, the root in shape for lugs is had easily to produce the trend of micropore.
For the roughening face of the metal forming of the present invention, it is shaped as elongated shape when the thrust utilizing roughening treatment to be formed
Time, there is the trend easily producing micropore, it is therefore preferable that the mean breadth of shape for lugs more than height 1 μm is the prominent of more than 1 μm
Playing shape and accounting for the ratio of whole shape for lugs is more than 10%, more preferably more than 30%.Wherein, the mean breadth of shape for lugs
Can be using the width of 1/2 height of shape for lugs as mean breadth.Should illustrate, the Copper Foil of the most roughened process city
Selling, the Copper Foil of the condition meeting roughening treatment face described in the present invention can obtain from commercially available product.
Ni, Zn and Cr carry out plating to preferred roughening treatment face, the roughening treatment face of metal forming, and Ni content is
0.1mg/dm2Above, and the Y value (brightness) that utilizes luminance meter to measure is more than 25.This brightness is to irradiate light to sample surfaces
And the volume reflection of light is worth as obtained by brightness, as the index of the roughness on finding surface.Brightness is low is to represent reflectance
Gap low, i.e. narrow and deep between adjacent thrust is many, easily generates micropore during thermo-compressed.Ni content is less than
0.1mg/dm2Time, owing to corrosion resistance is not enough, so unrelated with the fillibility of polyimides and by acid corrosion.
Then, illustrate with the polyimide layer forming insulating barrier in the metal-clad of the present invention.
As described above, in the present invention, for polyimide layer, it is necessary to polyimide layer (i) as with metal
The layer that paper tinsel connects, is preferably made up of multiple polyimides.When representing the configuration example of the most concrete polyimide layer, can illustrate
Following configuration example.Should illustrate, in following configuration example, M is the writing a Chinese character in simplified form of metal forming, PI is writing a Chinese character in simplified form of polyimides, additionally, PI layer
(i) be glass transition temperature be the polyimide layer of more than 300 DEG C, PI layer (ii) is that glass transition temperature compares polyimides
The polyimide layer of high more than 50 DEG C of layer (i).
1) M/PI layer (i)/PI layer (ii)/PI layer (i)
2) M/PI layer (i)/PI layer (ii)/PI layer (i)/M
3) M/PI layer (ii)/PI layer (i)/M
The polyimides constituting polyimide layer typically represents with following formula (1), it is possible to by using substantially equimolar
Diamine component and acid dianhydride component, the known method that carries out being polymerized in organic polar solvent manufacture.
Formula (1)
Wherein, Ar1For the organic group of 4 valencys of the aromatic ring with more than 1, Ar2For having the fragrance of more than 1
The organic group of the divalent of race's ring, n represents repeat number.That is, Ar1For the residue of acid dianhydride, Ar2Residue for diamidogen.
Solvent for the polymerization of polyimides such as can enumerate dimethyl acetylamide, N-Methyl pyrrolidone, 2-butanone,
Diethylene glycol dimethyl ether, dimethylbenzene etc., it is also possible to use a kind or and with two or more these compound.It addition, obtain for polymerization
The resin viscosity of polyamic acid (polyimide precursor), preferably in the scope of 500cps～35000cps.
On the basis of considering many characteristics that the composition polyimide layer (i) of insulating barrier, polyimide layer (ii) require,
The diamine component used as raw material and acid dianhydride component suitably select from each material composition of following illustration most suitable become
Point.
As acid dianhydride component, for example, it is preferable to by O (CO)2-Ar1-(CO)2Aromatic tetracarboxylic acid's dianhydride that O represents, permissible
Illustrate the aromatic anhydride residue that following formula (2) represented as Ar1And the aromatic tetracarboxylic acid's dianhydride formed.
Formula (2)
It addition, as diamidogen, the most preferably by H2N-Ar2-NH2The aromatic diamine represented, can illustrate following formula
(3) the aromatic diamine residue represented is as Ar2And the aromatic diamine formed.
Formula (3)
Polyimide layer (i) in the present invention be the glass transition temperature connected with metal forming be more than 300 DEG C poly-
Imide layer.From with the cementability of metal forming from the viewpoint of, polyimide layer (i) must with when adding thermo-compressed of metal forming
Display thermoplasticity, if but glass transition temperature step-down, then cause thermostability to reduce.From this viewpoint, preferably polyamides is sub-
The preferred glass transition temperature of amine layer (i) is less than 350 DEG C.
As the acid dianhydride component of the such polyimide layer (i) of composition, the aromatic series four that above-mentioned formula (2) illustrates can be enumerated
Carboxylic acid dianhydride, but preferably with pyromellitic acid anhydride (PMDA) for required composition, as main constituent, particularly preferably use 80
Mole more than %.It addition, as the diamine component of composition polyimide layer (i), the aromatic series two that above-mentioned formula (3) illustrates can be enumerated
Amine, particularly preferably with 2, double [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-is required composition, as main constituent,
Particularly preferably use 80 moles of more than %.Wherein, it is possible to by other acid dianhydride and diamine component and use two or more.
Polyimide layer (ii) glass transition temperature compared with polyimide layer (i) of the present invention is high more than 50 DEG C
Polyimide layer.From with the cementability of metal forming from the viewpoint of, preferably polyimide layer (ii) does not directly connect with metal forming
And it is integrated with metal forming via polyimide layer (i).
For constituting the acid dianhydride component of such polyimide layer (ii), it is preferably used selected from equal four benzoic acid dianhydrides
(PMDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,
3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride (DSDA) and 4, the compound in 4 '-4,4'-oxydiphthalic anhydride (ODPA), also
These individually or can be mixed two or more use.
For constituting the diamine component of such polyimide layer (ii), diaminodiphenyl ether (DAPE), 2 '-first can be illustrated
Epoxide-4,4 '-diaminobenzene anilid (MABA), 2,2 '-dimethyl-4,4 '-benzidine (m-TB), p-phenylenediamine
(P-PDA), 1, double (4-amino-benzene oxygen) benzene (TPE-R) of 3-, 1,3-double (3-amino-benzene oxygen) benzene (APB), Isosorbide-5-Nitrae-bis-(4-ammonia
Phenoxyl) benzene (TPE-Q) and 2, double [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-, can be by this as preference
A little individually or mix two or more and use.
The thickness of the polyimide layer of the present invention is preferably in the scope of 8～40 μm, further preferably at the model of 9～30 μm
Enclose.It addition, polyimide layer (i) plays the cementability kept with metal level, the linear expansion coefficient overall by controlling insulating barrier
And maintain the effect of balance, preferably its thickness is in the scope of 1～3 μm.Polyimide layer (i) can be arranged on polyimide layer
(ii) one or both sides.
As it has been described above, insulating barrier should be made up of the polyimide layer of single or multiple lift in the present invention, but in the present invention
In, preferably in insulating barrier overall (polyimide layer is overall) linear expansion coefficient (CTE) 10 × 10-6～25 × 10-6[1/K's]
Scope.When polyimide layer is set to multilamellar, the linear expansion coefficient (CTE) of the most above-mentioned polyimide layer (ii) is 30 × 10-6
[1/K] below, particularly preferably 1 × 10-6～20 × 10-6The scope of [1/K].It addition, now, polyimide layer (i) preferably exists
20×10-6～60 × 10-6The scope of [1/K], particularly preferably 30 × 10-6～50 × 10-6The scope of [1/K].
Hereinafter, above-mentioned configuration example 2 based on duplexer) [M/PI layer (i)/PI layer (ii)/PI layer (i)/M], to the present invention
The manufacture method of metal-clad illustrate.Should illustrate, in following example, M uses Copper Foil.
In this example, first, will be used for being formed the solution of the polyamic acid as polyimide precursor of polyimide layer (i)
Being coated directly onto the surface of the Copper Foil of roughening treatment, the temperature appropriateness removing below 150 DEG C contains in resin solution
Solvent.
Then, directly coating is used for being formed the polyamic acid as polyimide precursor molten of polyimide layer (ii)
Liquid, the temperature appropriateness below 150 DEG C removes the solvent contained in resin solution.
Followed by, directly coating is used for being formed the polyamic acid as polyimide precursor molten of polyimide layer (i)
Liquid, the temperature appropriateness below 150 DEG C removes the solvent contained in resin solution.So, Copper Foil forms appropriateness to remove
The polyimide precursor layer of the multilamellar of solvent, afterwards, and then at 100～450 DEG C, preferably the temperature range of 300～450 DEG C
Carry out the heat treatment of about 5～40 minutes, remove solvent further and carry out imidizate.
In this condition, Copper Foil defines the one side copper-clad laminated board being made up of 3 strata imide layer, at this one side
The side, polyimide layer (i) face of copper-clad laminated board adds the Copper Foil of thermo-compressed roughening treatment.Heating is crimped on compares polyimide layer
Carry out adding thermo-compressed i the glass transition temperature of () is slightly higher at a temperature of, in the present invention, by using above-mentioned specific roughening
The Copper Foil in process face, it is possible to the generation of suppression micropore.In this example, use the copper of roughening treatment in the both sides of polyimide layer
Paper tinsel, but in the present invention, the specific Copper Foil of above-mentioned regulation can be only used for one of which, preferably be only used for adding thermo-compressed side
Copper Foil.
So, using the layer connected with metal forming requiring thermostability in the present invention is the poly-of high glass-transition temperature
During imide layer, be there is by use the Copper Foil of the roughening treatment of specific surface texture, it is possible to maintain dimensional stability,
Under the state of other many characteristics of the metal-clads such as cementability, the generation of suppression micropore.
Embodiment
Hereinafter, the present invention is further described based on embodiment.Should illustrate, in the examples below, unless otherwise
Illustrate, for various evaluations by the following stated.
[mensuration of glass transition temperature]
Use SII Nano Technology company's dynamic determination of viscoelasticity device (RSA-III), will be to base material Copper Foil
It is etched the polyimides becoming membrane stage and carries out the temperature dispersion mensuration of 1.0Hz, tan mensuration obtained with stretch mode
The peak value of δ is set to glass transition temperature.
[evaluation in roughening treatment face]
The shape evaluation in roughening treatment face utilizes FE-SEM (Hitachi High-Technologies company S-4700
Type) the Copper Foil cross section that makes of observation Cross section polishing instrument (NEC company SM-09010), in the range of wide 25 μm
The shape in roughening portion is evaluated.
It addition, the Ni for roughening treatment face measures, only make the face connected with polyimides surely be dissolved in 1N-nitric acid and use ICP-
AES (Perkin Elmer company Optima 4300) is measured.Additionally, lightness Y uses Suga testing machine company SM-4
It is measured.
[acid proof mensuration]
Acid proof being determined as follows is carried out, and for flexible single-sided copper-clad laminated board, carries out circuit fabrication with line width 1mm,
In 18wt% salt aqueous acid, 50 DEG C impregnate 60 minutes, then use 200 times of optical microscopes from insulating barrier (polyimides
Layer) circuit end measures because hydrochloric acid penetrates into the variable color width that causes by side.Wherein, hydrochloric acid penetrates into width is commenting of below 200 μm
Valency is good.
[mensuration of bonding force (peel strength)]
Bonding force between Copper Foil and polyimides is carried out as follows mensuration, for being formed by polyimide resin on Copper Foil
The flexible single-sided copper-clad laminated board that the insulating barrier constituted obtains, carries out circuit fabrication with line width 1mm, uses Toyo Seiki strain formula
Commercial firm's cupping machine (Strograph-M1), peels off Copper Foil along 180 ° of directions, measures initial stage peel strength.It addition, on Ce Dinging
State the peel strength after acid resistance measures, using acidproof rear peel strength/initial stage peel strength × 100 as conservation rate.
Synthesis example 1
In possessing thermocouple and blender and the reaction vessel of nitrogen can be imported, add N,N-dimethylacetamide.?
By 2 in this reaction vessel, limit is stirred on propane (BAPP) limit to 2-double [4-(4-amino-benzene oxygen) phenyl] in a reservoir makes it dissolve.
Then, add pyromellitic acid dianhydride (PMDA), make the otal investment of monomer become 12wt%.Afterwards, continue stirring 3 hours,
Resin solution b to polyamic acid.The solution viscosity of the resin solution b of polyamic acid is 3,000cps.Obtained by this polyamic acid
To polyimides be showed more than 30 × 10-6(1/K) linear expansion coefficient, has the glass transition temperature of 315 DEG C.
Synthesis example 2
In possessing thermocouple and blender and the reaction vessel of nitrogen can be imported, add N,N-dimethylacetamide.?
By 2,2 '-dimethyl-4 in this reaction vessel, limit is stirred on 4 '-benzidine (m-TB) limit in a reservoir makes it dissolve.Then,
Add 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) and pyromellitic acid dianhydride (PMDA).So that the otal investment of monomer becomes
15wt%, the molar ratio (BPDA: PMDA) of each anhydride become the mode of 20: 80 and put into.Afterwards, continue stirring 3 hours, obtain
The resin solution a of polyamic acid.The solution viscosity of the resin solution a of polyamic acid is 20,000cps.Obtained by this polyamic acid
Polyimides show 20 × 10-6(1/K) linear expansion coefficient below, has the character of non-thermal plasticity.
Embodiment 1
As Copper Foil, prepare as the surface-treated layer silane coupler with amino carried out silane coupled process,
And there is the electrolytic copper foil in the roughening treatment face shown in table 1.This copper thickness is 12 μm, and surface roughness (Rz) is 1.2 μm.Will
The resin solution a of the polyamic acid prepared in the resin solution b of polyamic acid of preparation, synthesis example 1 in synthesis example 2 and synthesis example
In 2, the resin solution b of the polyamic acid of preparation is coated on this Copper Foil, successively after drying, finally at 300 DEG C carried out above about 10
Minute heat treatment, the thickness obtaining polyimides is the flexible single-sided copper-clad laminated board of 25 μm.Should illustrate, polyimide layer has
Have 21 μm obtained by the resin solution a of polyamic acid layer and in its both sides by the resin solution b of polyamic acid obtain each
The layer of 2 μm.
For the flexible single-sided copper-clad laminated board so obtained, Copper Foil similar to the above is added pressure in heating and passes through
Between metal roller thus carry out further adding thermo-compressed with its polyimides aspect.Peel strength and acid proof evaluating characteristics
The heating electrolysis side of flexible two sides copper-clad laminated board is carried out, at the beginning of the 1mm between result Copper Foil and polyimide layer peels off
Phase bonding force is 1.95kN/m.It addition, the infiltration width of acid resisting test based on this circuit is 69 μm, peel strength conservation rate
It is 89%.Result is shown in table 2.
Embodiment 2,3, comparative example 1,2
Use the electrolytic copper foil shown in table 1 that surface metal amount is different, carry out the most similarly to Example 1, comment
Valency peel strength, hydrochloric acid accessibility, stripping conservation rate.Result is shown in table 2.
Though being not illustrated in table 1, but enter with Ni, Zr and Cr in the roughening treatment face of embodiment, whole Copper Foils of comparative example use
Row plating.
In table 1,
B the bump counts of () high-aspect-ratio number/all represent relative to the whole bump counts measured, length-width ratio (H/L) 1.5～
The scope of 5 and rising height are in the ratio of the projection quantity of the scope of 1～3 μm.
C the close clearance number between () projection/whole bump counts represent relative to the whole bump counts measured, adjacent projection
Between thing, the degree of depth is more than 0.5 μm and the abutment lug thing spacing ratio in the quantity in the gap of 0.001～1 μ m.
It addition, (d) expands bump count/whole bump counts is relative to the whole bump counts measured, have than root width L
The ratio of broader shape for lugs quantity.
Additionally, more than (e) projection mean breadth 1 μm/all bump counts be relative to the whole bump counts measured, projection
Mean breadth is the ratio of the projection quantity of more than 1 μm.
Should illustrate, the photo in Copper Foil cross section, the reference in figure 3 used in embodiment 1 is shown to referential in fig. 2
Property the photo in Copper Foil cross section used in comparative example 2 is shown.Wherein, the Copper Foil used in embodiment 2 and 3, the copper that Rz is different
The trickle roughening shape on the surface of paper tinsel is similar with Fig. 2；The Copper Foil used in comparative example 1, the surface of the Copper Foil that Rz is different trickle
Roughening shape is similar with Fig. 3.
[table 1]
[table 2]
For the copper-clad laminated board obtained in embodiment 1,2,3, can confirm that the variable color of the circuit end after HCl treatment is
Below 200 μm, peel strength conservation rate is more than 70%.On the other hand, in comparative example 1,2, in circuit end, entirety can confirm that
Because circuit peels off the variable color caused, peel strength conservation rate is less than 70%.
So can confirm that, the flexible copper-clad laminate obtained in the present invention is due to oozing after can suppressing HCl treatment
Entering, not producing circuit stripping, so being the material that reliability is high.
Claims (6)
1. a metal-clad, it is characterised in that the one or two sides at polyimide layer has metal forming, with described gold
Belonging to the glass transition temperature of polyimide layer (i) that paper tinsel connects is more than 300 DEG C, described metal forming with polyimide layer phase
The roughening treatment face connect meets following condition (a)～(c)
Surface roughness Rz in (a) roughening treatment face in the scope of 0.5～4 μm,
B the skin section in () roughening treatment face is the micro crowning shape formed by multiple roughening particles, with described micro crowning shape
Length-width ratio H/L that the ratio of the rising height H and root width L of 1 thrust of shape represents is at 1.5～5 scope and rising heights
It is less than 50% in the ratio of shape for lugs of 1～3 μ m relative to the quantity of whole shape for lugs,
The degree of depth in c gap that () is formed between thrust adjacent to each other is more than 0.5 μm and the entire depth side in this gap
To, the adjacent distance between thrust in the gap of 0.001～1 μ m quantity is whole shape for lugs number 50% with
Under.
Metal-clad the most according to claim 1, wherein, in claim 1 (b) in the shape for lugs of regulation,
The ratio of the shape for lugs that there is the width bigger than root width L towards zenith directions relative to the quantity of whole shape for lugs is
Less than 20%.
Metal-clad the most according to claim 1 and 2, wherein, the mean breadth of shape for lugs more than highly 1 μm
It is that to account for the ratio of whole shape for lugs be more than 10% for the shape for lugs of more than 1 μm.
Metal-clad the most according to claim 1 and 2, wherein, roughening treatment face Ni, Zn and Cr carry out plating
Processing, Ni content is 0.1mg/dm2Above, and the Y value i.e. brightness that utilizes luminance meter to measure is more than 25.
Metal-clad the most according to claim 1 and 2, wherein, polyimide layer is made up of multilamellar, with metal forming not
The glass transition temperature of the polyimide layer (ii) connected is than the vitrification of the polyimide layer (i) connected with described metal forming
Transition temperature is high more than 50 DEG C.
Metal-clad the most according to claim 1 and 2, wherein, polyimide resin layer and metal forming are at 1mm width
Under initial bond power be more than 1.0kN/m, impregnating the peel strength conservation rate after 1 hour in hydrochloric acid is more than 80%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011080333A JP5698585B2 (en) | 2011-03-31 | 2011-03-31 | Metal-clad laminate |
| JP2011-080333 | 2011-03-31 |
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| Publication Number | Publication Date |
|---|---|
| CN102740613A CN102740613A (en) | 2012-10-17 |
| CN102740613B true CN102740613B (en) | 2016-09-14 |
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| CN201210093700.0A Active CN102740613B (en) | 2011-03-31 | 2012-03-31 | Metal-clad |
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| JP (1) | JP5698585B2 (en) |
| KR (1) | KR101965174B1 (en) |
| CN (1) | CN102740613B (en) |
| TW (1) | TWI528872B (en) |
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| JP2016215651A (en) * | 2016-07-19 | 2016-12-22 | 新日鉄住金化学株式会社 | Flexible copper-clad laminated sheet and flexible circuit board |
| KR102353143B1 (en) * | 2017-07-24 | 2022-01-18 | 후루카와 덴키 고교 가부시키가이샤 | Surface-treated copper foil and copper clad laminate and printed wiring board using the same |
| CN114007832B (en) * | 2019-06-17 | 2024-04-19 | 株式会社可乐丽 | Method for producing metal-clad laminate |
| CN114953640B (en) * | 2022-05-27 | 2023-10-20 | 广州方邦电子股份有限公司 | Flexible metal-clad plate, electronic device and manufacturing method of flexible metal-clad plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0650794B2 (en) | 1989-05-02 | 1994-06-29 | 日鉱グールド・フォイル株式会社 | Method of treating copper foil for printed circuits |
| JPH0693537A (en) | 1992-09-07 | 1994-04-05 | Kanebo Ltd | Loom management apparatus |
| JP2717910B2 (en) | 1992-11-19 | 1998-02-25 | 日鉱グールド・フォイル株式会社 | Copper foil for printed circuit and manufacturing method thereof |
| JP2875186B2 (en) | 1995-06-08 | 1999-03-24 | 日鉱グールド・フォイル株式会社 | Processing method of copper foil for printed circuit |
| TWI300744B (en) | 2001-04-19 | 2008-09-11 | Nippon Steel Chemical Co | |
| JP4615226B2 (en) * | 2004-02-06 | 2011-01-19 | 古河電気工業株式会社 | Composite material for substrate and circuit board using the same |
| JP4692758B2 (en) * | 2006-02-24 | 2011-06-01 | 信越化学工業株式会社 | Flexible laminate and method for manufacturing the same |
| JP2007281361A (en) * | 2006-04-11 | 2007-10-25 | Asahi Kasei Corp | Polyimide printed circuit board and polyimide printed wiring board |
| EP2319960A4 (en) * | 2008-07-22 | 2013-01-02 | Furukawa Electric Co Ltd | Flexible copper-clad laminate |
| JP5180814B2 (en) * | 2008-12-26 | 2013-04-10 | 新日鉄住金化学株式会社 | Laminated body for flexible wiring board |
| KR101722430B1 (en) * | 2009-07-24 | 2017-04-03 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Regin composite electrolytic copper foil, copper clad laminate and printed wiring board |
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2011
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2012
- 2012-03-13 TW TW101108417A patent/TWI528872B/en active
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| Publication number | Publication date |
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| TWI528872B (en) | 2016-04-01 |
| CN102740613A (en) | 2012-10-17 |
| KR20120112216A (en) | 2012-10-11 |
| KR101965174B1 (en) | 2019-04-03 |
| JP5698585B2 (en) | 2015-04-08 |
| TW201251535A (en) | 2012-12-16 |
| JP2012213902A (en) | 2012-11-08 |
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