CN102740613A - Metal-clad laminate - Google Patents
Metal-clad laminate Download PDFInfo
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- CN102740613A CN102740613A CN2012100937000A CN201210093700A CN102740613A CN 102740613 A CN102740613 A CN 102740613A CN 2012100937000 A CN2012100937000 A CN 2012100937000A CN 201210093700 A CN201210093700 A CN 201210093700A CN 102740613 A CN102740613 A CN 102740613A
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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
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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
- 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
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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
- 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
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Abstract
The invention provides a metal-clad laminate, which is advantageous in that, on the basis of size stability, heat resistance is excellent, and particularly when micropores generated between layers at the heating and pressurizing side are inhibited, adhesion reliability is also excellent. For the laminate, glass-transition temperature of a polyimide layer connected with a metal foil is more than 300 DEG C, and the roughening surface of the metal foil is designed in such a way that: (a) the surface roughness Rz is 0.5-4 [mu]m; (b) a plurality of fine protruding shapes are formed at the surface layer part of the roughening surface, the length-width ratio H/L represented by the ratio of the protruding height H to the root width L of one projection is in the range of 1.5-5, the proportion of the protruding shapes with the protruding height in the range of 1-3 [mu]m is less than 50% relative to all the protruding shapes; and (c) the proportion of projections with the depth between the projections being more than 0.5 [mu]m, and gaps of adjacent projections in the range of 0.001-1 [mu]m relative to all the protruding shapes is less than 50%.
Description
Technical field
The present invention relates to be fit to be used in flexible circuit board metal-clad, relate in particular to insulating barrier and have a flexible flexible metal-coated lamination by what polyimide resin formed.
Background technology
In recent years; Be accompanied by high performance, miniaturization and the lightweight of mobile phone, digital camera, DV, PDA, automobile navigation instrument, hard disk, other various electronic equipments; Electric distribution as them is used baseplate material, replace the rigid substrates that in the past always used and adopt the degree of freedom of distribution high, example that be easy to the flexible printed board of slimming increases gradually.And, for for flexible printed board development, that be used for these equipment of High Level more, more small-sized densification, multiple stratification, become more meticulous, high heat-resistingization etc. require progressively to improve.
In order to respond these requirements; Disclose on conductor directly coating in patent documentation 1 grade and formed polyimide resin layer and carry out multiple stratification and form the different a plurality of polyimide resin layers of thermal coefficient of expansion, the method for the excellent flexible printed board of aspect reliabilities such as dimensional stability, bonding force and the flatness after etching to variations in temperature is provided thus.
For the copper-clad laminated board that does not have bond layer that uses in such flexible printed board; For example; As record such as patent documentation 2, patent documentation 3, patent documentation 4, use the copper foil surface Copper Foil of roughening treatment with the bonding force of resin bed in order to improve.
Yet; In recent years; In order to tackle the rising that is accompanied by unleaded solder joints temperature; As patent documentation 5 record, with high heat-resistingization of polyimide resin layer that Copper Foil joins, the infiltration of the sour cleaning fluid when between Copper Foil and polyimide layer, generating micropore, circuit fabrication easily when having thermo-compressed thus such as causes taking place that distribution peels off at the problem that bonding reliability reduces.For this problem, as patent documentation 6 records, the method for the coating layer that suppresses roughening treatment height, control Copper Foil roughening treatment face is arranged, but according to this method, possible initial stage peel strength can reduce, unresolved technical problem.
Patent documentation 1: the special fair 6-93537 communique of Japan
Patent documentation 2: japanese kokai publication hei 2-292894 communique
Patent documentation 3: japanese kokai publication hei 6-169168 communique
Patent documentation 4: japanese kokai publication hei 8-335775 communique
Patent documentation 5:WO2002/085616
Patent documentation 6:WO2010/010892
Summary of the invention
The object of the present invention is to provide a kind of metal-clad; For this metal-clad; Although the polyimide layer that joins with the metal forming of roughening treatment has high-fire resistance, the micropore that has suppressed between metal forming and polyimide layer, to generate and suppressed the circuit that the infiltration because of sour cleaning fluid causes through the bonding reliability that improves metal level and polyimide layer and peel off.
The inventor etc. further investigate in order to solve above-mentioned problem; The result finds that the alligatoring proterties through using metal foil surface is the metal-clad of peculiar proterties; The resin that will have particular characteristics is used for the polyimide resin that joins with this metal forming; Thereby can solve the problems of the technologies described above, until having accomplished the present invention.
Promptly; The present invention relates to a kind of metal-clad; It is characterized in that; Single face or two sides at polyimide layer have metal forming, and the glass transition temperature of the polyimide layer (i) that joins with above-mentioned metal forming is more than 300 ℃, and the roughening treatment face that joins with polyimide layer of above-mentioned metal forming satisfies following condition (a)～(c).
(a) surface roughness of roughening treatment face (Rz) is in the scope of 0.5～4 μ m
(b) skin section of roughening treatment face is the micro crowning shape that is formed by a plurality of alligatoring particles, and the length-width ratio of representing with the rising height H and the ratio of root width L of 1 thrust of above-mentioned micro crowning shape (H/L) is 50% below in the ratio of the shape for lugs of the scope of 1～3 μ m with respect to the quantity of whole shape for lugs at 1.5～5 scope and rising height
(c) be that the exist ratio of distance in the gap of the scope of 0.001～1 μ m is below 50% of whole shape for lugs numbers more than the 0.5 μ m and between the abutment lug thing in the degree of depth between the thrust of adjacency
Metal-clad of the present invention; The polyimides that not only constitutes insulating barrier has thermal endurance, show excellent size stability, can also be suppressed at metal forming and and its polyimide layer that joins between chemical reagent resistance when producing the circuit fabrication of micropore, flexible wiring sheet etc. also excellent, so be applicable to that circuit substrate, its serviceability of requiring high retrofit are very high.
Description of drawings
Fig. 1 is the ideograph of alligatoring shape that is used to explain the Copper Foil cross section of Copper Foil.
Fig. 2 is the Copper Foil cross-section photograph of the Copper Foil of use among the embodiment 1.
Fig. 3 is the Copper Foil cross-section photograph of the Copper Foil of use in the comparative example 2.
Symbol description
The width of the root of L micro crowning shape
The height of H micro crowning shape
1 thrust of p and q adjacency
1 thrust of q and p adjacency
Embodiment
Below specify the present invention.
Metal-clad of the present invention has metal forming on the single face or the two sides of polyimides.For polyimide layer; The glass transition temperature that needs only the polyimide layer that joins with metal forming is more than 300 ℃; Then can be that individual layer also can form by a plurality of layers; But be that polyimide layer (i) and other polyimide layer more than 300 ℃ forms by glass transition temperature preferably, other polyimide layer is (ii) formed by the polyimide resin layer that has than the high glass transition temperature more than 50 ℃ of glass transition temperature of polyimide layer (i).As metal forming, so long as state the surface coarsening shape after showing, its kind is just not special to be limited, but is 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 μ m, if consider the applicability to flexible wiring substrate, then more preferably in the scope of 9～30 μ m.
The roughening treatment face that joins with polyimide layer of the metal forming of using among the present invention must satisfy following condition (a)～(c).
(a) surface roughness of roughening treatment face (Rz) is in the scope of 0.5～4 μ m
(b) skin section of roughening treatment face is the micro crowning shape that is formed by a plurality of alligatoring particles, and the length-width ratio of representing with the rising height H and the ratio of root width L of 1 thrust of above-mentioned micro crowning shape (H/L) is 50% below in the ratio of the shape for lugs of the scope of 1～3 μ m with respect to the quantity of whole shape for lugs at 1.5～5 scope and rising height
(c) be that the exist ratio of distance in the gap of the scope of 0.001～1 μ m is below 50% of whole shape for lugs numbers more than the 0.5 μ m and between the abutment lug thing in the degree of depth between the thrust of adjacency
At first, must make the scope of the surface roughness (Rz) of roughening treatment face at 0.5～4 μ m.If the value less than of Rz 0.5 μ m, then the bonding force of metal forming and polyimide layer reduces; If surpass 4 μ m, etch residue increases when then circuit fabrication being become fine pattern, and its result's electricity reliability reduces.Here, the surface roughness of roughening treatment face (Rz) is meant the Rz of the definition regulation of " 5.1 ten mean roughness " that " be shown as the definition of surface roughness " at JISB 0601-1994.
Then; The skin section that must make roughening treatment face is the micro crowning shape that is formed by many alligatoring particles, and the length-width ratio of representing with the rising height H and the ratio of root width L of 1 thrust of above-mentioned micro crowning shape (H/L) is 50% below in the ratio of the shape for lugs of the scope of 1～3 μ m with respect to the quantity of whole shape for lugs at 1.5～5 scope and rising height.If the condition of above-mentioned length-width ratio and rising height surpasses 50%, then because the roughening of surface coarsening shape, so when the high polyimide layer of thermal endurance (glass transition temperature) added thermo-compressed, illiquidity generated micropore easily.
And then, for the roughening treatment face of metal foil surface, be that the exist ratio of distance in the gap of the scope of 0.001～1 μ m is necessary for below 50% of whole shape for lugs numbers more than the 0.5 μ m, between the abutment lug thing in the degree of depth between the thrust of adjacency.If this ratio surpasses 50%, then can not carry out the filling of resin fully to the gap, generate micropore easily.
Here, the roughening treatment of the metal forming of using for the present invention utilizes Fig. 1 to describe.Fig. 1 is with the surface portion amplification in metal forming cross section and the figure of medelling ground expression.Among the present invention, for example by shown in Figure 1, the length-width ratio of the micro crowning shape of roughening treatment face is the value that obtains divided by the root width L of thrust with the height H of 1 thrust of micro crowning shape.Rising height is meant the value of the length that expression is the longest apart from the center of the valley portions that connects adjacency.
In addition, for above-mentioned condition of the present invention (c), be the gap more than the 0.5 μ m, to judge apart from the ratio that exists that is the gap of 0.001～1 μ m between the abutment lug thing in this gap having the degree of depth between the thrust of adjacency.Among Fig. 1, thrust p and thrust q are the thrusts of adjacency, between thrust p and q, have the gap of the above degree of depth of 0.5 μ m.And distance is in the scope of 0.001～1 μ m between this adjacency.Gap such among the present invention is preferably less; If with condition (c) in other words, then as the degree of depth between thrust be the gap of the above degree of depth of 0.5 μ m and until between the adjacency till this degree of depth distance be the quantity below 50% in the gap of the scope of 0.001～1 μ m with respect to whole shape for lugs numbers.
It is below 20% with respect to the quantity of whole shape for lugs that preferably there is the ratio of the shape for lugs of the width bigger than root width L in the alligatoring shape that the metal foil surface of using in the present invention forms towards zenith directions, more preferably below 10%.When this ratio surpasses 20%, the trend that is easy to generate micropore at the root of shape for lugs is arranged.
Alligatoring face for metal forming of the present invention; When the thrust that utilizes roughening treatment to form be shaped as elongated shape the time; The trend that is easy to generate micropore is arranged; Therefore, the mean breadth of the shape for lugs that preferred heights 1 μ m is above is that the ratio that the above shape for lugs of 1 μ m accounts for whole shape for lugs is more than 10%, more preferably more than 30%.Wherein, the mean breadth of shape for lugs can with shape for lugs 1/2 the height width as mean breadth.Should explain that commercially available through the Copper Foil of roughening treatment like this, the said Copper Foil that satisfies the condition of roughening treatment face of the present invention can obtain from commercially available article.
The preferred roughening treatment face of the roughening treatment face of metal forming carries out plating with Ni, Zn and Cr to be handled, and Ni content is 0.1mg/dm
2More than, and the Y value (brightness) of utilizing luminance meter to measure is more than 25.This brightness be to the sample surfaces irradiates light and with the reflection of light amount as brightness and value, as the index of the roughness on finding surface.Brightness is low to be that the expression reflectivity is low, promptly narrow and dark gap is many between the thrust of adjacency, the micropore when generating thermo-compressed easily.Ni content is lower than 0.1mg/dm
2The time, because corrosion resistance is not enough, so irrelevant and by acid corrosion with the fillibility of polyimides.
Then, to describing with the polyimide layer that forms insulating barrier in the metal-clad of the present invention.
As above state bright that kind, among the present invention, for polyimide layer, the layer that must polyimide layer (i) conduct joins with metal forming preferably is made up of a plurality of polyimides.When the formation of the polyimide layer that expression is preferred concrete is routine, but the following formation example of illustration.Should explain; In the following formation 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, in addition; PI layer (i) is the polyimide layer more than 300 ℃ for glass transition temperature, and the PI layer (ii) is that glass transition temperature is than the high polyimide layer more than 50 ℃ of polyimide 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) the M/PI layer (ii)/PI layer (i)/M
The polyimides that constitutes polyimide layer is generally with following formula (1) expression, can make through the known method that uses equimolar in fact two amine components and acid dianhydride composition, in organic polar solvent, carries out polymerization.
Wherein, Ar
1Be the organic group of 4 valencys, Ar with the aromatic ring more than 1
2Be the organic group of divalent with the aromatic ring more than 1, n representes repeat number.That is Ar,
1Be the residue of acid dianhydride, Ar
2Residue for diamines.
The solvent that is used for the polymerization of polyimides for example can be enumerated dimethylacetylamide, N-methyl pyrrolidone, 2-butanone, diethylene glycol dimethyl ether, xylenes etc., can also use a kind or and with these compounds more than 2 kinds.In addition, the resin viscosity of the polyamic acid (polyimide precursor) that obtains for polymerization is preferably in the scope of 500cps～35000cps.
On the basis that consider to constitute the polyimide layer (i) of insulating barrier, many characteristics that polyimide layer (ii) requires, two amine components that use as raw material and the acid dianhydride composition suitable only composition of selection from following illustrative each material composition.
As the acid dianhydride composition, for example, preferably by O (CO)
2-Ar
1-(CO)
2Aromatic tetracarboxylic acid's dianhydride that O representes, can illustration with the aromatic anhydride residue of following formula (2) expression as Ar
1And the aromatic tetracarboxylic acid's dianhydride that forms.
Formula (2)
In addition, as diamines, for example preferably by H
2N-Ar
2-NH
2The aromatic diamine of expression, can illustration with the aromatic diamine residue of following formula (3) expression as Ar
2And the aromatic diamine that forms.
Formula (3)
Polyimide layer among the present invention (i) is that the glass transition temperature that joins with metal forming is the polyimide layer more than 300 ℃.From with the viewpoint of the cementability of metal forming, polyimide layer (i) must with metal forming add thermo-compressed the time show thermoplasticity, if but the glass transition temperature step-down then causes thermal endurance to reduce.From this viewpoint, the preferred glass transition temperature of preferred polyimide layer (i) is lower than 350 ℃.
As the acid dianhydride composition that constitutes such polyimide layer (i), can enumerate the illustrative aromatic tetracarboxylic acid's dianhydride of above-mentioned formula (2), but be essential composition preferably with pyromellitic acid anhydride (PMDA), it as principal component, is especially preferably used 80 moles more than the %.In addition, as two amine components that constitute polyimide layer (i), can enumerate the illustrative aromatic diamine of above-mentioned formula (3); Especially preferably with 2; Two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-are essential composition, and it as principal component, is especially preferably used 80 moles more than the %.Wherein, also can be with other acid dianhydride and two amine components and with more than 2 kinds.
Polyimide layer of the present invention (ii) is to compare the high polyimide layer more than 50 ℃ of glass transition temperature with polyimide layer (i).From with the viewpoint of the cementability of metal forming, preferred polyimide layer does not (ii) directly join and is situated between integrated by polyimide layer (i) and metal forming with metal forming.
For constituting such polyimide layer acid dianhydride composition (ii), the preferred use is 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 '-diphenyl sulfone tetracarboxylic dianhydride (DSDA) and 4, the compound in 4 '-4,4'-oxydiphthalic anhydride (ODPA) also can be with these separately or mix more than 2 kinds and use.
For constituting such polyimide layer two amine components (ii); But illustration diaminodiphenyl ether (DAPE), 2 '-methoxyl group-4,4 '-diaminobenzene anilid (MABA), 2,2 '-dimethyl-4; 4 '-benzidine (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) and 2 of 4-; Two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-are as preference, can be with these separately or mix more than 2 kinds and use.
The thickness of polyimide layer of the present invention is preferably in the scope of 8～40 μ m, further preferably in the scope of 9～30 μ m.In addition, polyimide layer (i) plays and keeps with the cementability of metal level, keeps the effect of balance through the whole coefficient of linear expansion of control insulating barrier, and preferably its thickness is in the scope of 1～3 μ m.Polyimide layer (i) can be arranged on polyimide layer one or both sides (ii).
As stated, insulating barrier should be made up of the polyimide layer of single or multiple lift in the present invention, but in the present invention, coefficient of linear expansion (CTE) is 10 * 10 in the preferred insulating barrier whole (polyimide layer is whole)
-6～25 * 10
-6The scope of [1/K].When polyimide layer was made as multilayer, preferred above-mentioned polyimide layer coefficient of linear expansion (CTE) (ii) was 30 * 10
-6Below [1/K], particularly preferably in 1 * 10
-6～20 * 10
-6The scope of [1/K].In addition, at this moment, polyimide layer (i) is preferably 20 * 10
-6～60 * 10
-6The scope of [1/K] is particularly preferably in 30 * 10
-6～50 * 10
-6The scope of [1/K].
Below, based on the above-mentioned formation example 2 of duplexer) [M/PI layer (i)/PI layer (ii)/PI layer (i)/M], the manufacturing approach of metal-clad of the present invention is described.Should explain that in following example, M uses Copper Foil.
In this example, at first, the solution as the polyamic acid of polyimide precursor that will be used to form polyimide layer (i) directly is coated on the surface of the Copper Foil of roughening treatment, removes the solvent that in resin solution, contains in the temperature appropriateness below 150 ℃.
Then, directly coating is used to form the polyimide layer solution as the polyamic acid of polyimide precursor (ii), removes the solvent that in resin solution, contains in the temperature appropriateness below 150 ℃.
Follow, directly coating is used to form the solution as the polyamic acid of polyimide precursor of polyimide layer (i), removes the solvent that in resin solution, contains in the temperature appropriateness below 150 ℃ again.Like this, on Copper Foil, form appropriateness and removed the polyimide precursor layer of the multilayer of solvent, afterwards, and then 100～450 ℃, preferably carry out the heat treatment about 5～40 minutes 300～450 ℃ temperature range, further remove and desolvate and carry out imidizate.
Under this state, on Copper Foil, formed the single face copper-clad laminated board that constitutes by 3 strata imide layer, add the thermo-compressed Copper Foil of roughening treatment in polyimide layer (i) the face side of this single face copper-clad laminated board.Heating is crimped on than adding thermo-compressed under the high slightly temperature of the glass transition temperature of polyimide layer (i), in the present invention, through using the Copper Foil of above-mentioned specific roughening treatment face, can suppress the generation of micropore.In this example, use the Copper Foil of roughening treatment in the both sides of polyimide layer, but among the present invention, can the specific Copper Foil of afore mentioned rules only be used for wherein one, preferably only be used to add the Copper Foil of thermo-compressed side.
Like this; When the stable on heating layer that joins with metal forming of instructions for use in the present invention is the polyimide layer of high glass-transition temperature; The Copper Foil that has the roughening treatment of specific surface texture through use; Can under the state of other many characteristics of keeping metal-clads such as dimensional stability, cementability, suppress the generation of micropore.
Embodiment
Below, based on embodiment further explain the present invention.Should explain, in following examples, except as otherwise noted, press the following stated for various evaluations.
[mensuration of glass transition temperature]
Use SII Nano Technology corporate system Measurement of Dynamic Viscoelasticity device (RSA-III); To measure with the temperature dispersion that stretch mode carries out 1.0Hz the polyimides that the base material Copper Foil carries out etching and becomes membrane stage, the peak value of the tan δ that mensuration is obtained is made as glass transition temperature.
[evaluation of roughening treatment face]
The shape evaluation of roughening treatment face utilizes FE-SEM (Hitachi High-Technologies corporate system S-4700 type) to observe and polishes appearance (the corporate system SM-09010 of NEC) copper foil manufactured cross section with the cross section, and the shape of the alligatoring portion in the scope of wide 25 μ m is estimated.
In addition, the Ni amount for roughening treatment face only makes the face that joins with polyimides be dissolved in surely in the 1N-nitric acid and measures with ICP-AES (Perkin Elmer corporate system Optima 4300).In addition, lightness Y uses Suga testing machine corporate system SM-4 to measure.
[acid proof mensuration]
Acid proof mensuration is carried out as follows; For flexible single-sided copper-clad laminated board; Carry out circuit fabrication with line width 1mm; 50 ℃ flooded 60 minutes in the 18wt% aqueous solution of hydrochloric acid, used 200 times of light microscopes the circuit end to be measured the variable color width that causes because of the hydrochloric acid infiltration from insulating barrier (polyimide layer) side then.Wherein, hydrochloric acid infiltration width is being evaluated as well below the 200 μ m.
[mensuration of bonding force (peel strength)]
Bonding force between Copper Foil and the polyimides is measured as follows; The flexible single-sided copper-clad laminated board that the insulating barrier that is made up of polyimide resin for formation on Copper Foil obtains; Carry out circuit fabrication with line width 1mm; Use the smart machine Co., Ltd.'s cupping machine (Strograph-M1) of Japan, peel off Copper Foil, measure the initial stage peel strength along 180 ° of directions.In addition, measure the peel strength after above-mentioned acid resistance is measured, with acidproof back peel strength/initial stage peel strength * 100 as conservation rate.
Synthetic example 1
Possessing thermocouple and mixer and can import in the reaction vessel of nitrogen, adding N, the N-dimethylacetylamide.With 2, the limit is stirred on propane (BAPP) limit to 2-two [4-(4-amino-benzene oxygen) phenyl] in container make its dissolving in this reaction vessel.Then, add pyromellitic acid dianhydride (PMDA), make the otal investment of monomer become 12wt%.Afterwards, continue to stir 3 hours, obtain the resin solution b of polyamic acid.The solution viscosity of the resin solution b of polyamic acid is 3,000cps.The polyimides that is obtained by this polyamic acid shows above 30 * 10
-6Coefficient of linear expansion (1/K) has 315 ℃ glass transition temperature.
Synthetic example 2
Possessing thermocouple and mixer and can import in the reaction vessel of nitrogen, adding N, the N-dimethylacetylamide.In this reaction vessel with 2,2 '-dimethyl-4,4 '-benzidine (m-TB) limit is stirred the limit and is made its dissolving in container.Then, add 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA) and pyromellitic acid dianhydride (PMDA).So that the otal investment of monomer becomes the molar ratio (BPDA: PMDA) become 20: 80 mode and drop into of 15wt%, each acid anhydrides.Afterwards, continue to stir 3 hours, obtain the resin solution a of polyamic acid.The solution viscosity of the resin solution a of polyamic acid is 20,000cps.The polyimides that is obtained by this polyamic acid shows 20 * 10
-6Coefficient of linear expansion (1/K) has the character of non-thermal plasticity.
Embodiment 1
As Copper Foil, prepare as surface-treated layer with having the electrolytic copper foil that amino silane coupler has carried out silane coupled processing and had the roughening treatment face shown in the table 1.This copper thickness is 12 μ m, and surface roughness (Rz) is 1.2 μ m.The resin solution b of the polyamic acid for preparing in the resin solution b of the polyamic acid of preparation in the synthetic example 2, the resin solution a that synthesizes the polyamic acid of preparation in the example 1 and the synthetic example 2 is coated on this Copper Foil successively; After the drying; Carrying out heat treatment in about 10 minutes more than 300 ℃ at last, the thickness that obtains polyimides is the flexible single-sided copper-clad laminated board of 25 μ m.Should explain that polyimide layer has the layer of the 21 μ m that the resin solution a by polyamic acid obtains and the layer of each 2 μ m of being obtained by the resin solution b of polyamic acid in its both sides.
For the flexible single-sided copper-clad laminated board that obtains like this, thereby will under heating and pressurizing, further add thermo-compressed with above-mentioned same Copper Foil through metal roll shop building and its polyimides aspect.Peel strength and acid proof evaluating characteristics carry out the thermo-compressed face side that adds of flexible two sides copper-clad laminated board, and the initial stage bonding force peeled off of the 1mm between Copper Foil and the polyimide layer is 1.95kN/m as a result.In addition, be 69 μ m based on the infiltration width of the acid resisting test of this circuit, the peel strength conservation rate is 89%.The result is shown in table 2.
Embodiment 2,3, comparative example 1,2
Use the electrolytic copper foil shown in the different table 1 of surface metal amount, in addition likewise carry out, estimate peel strength, hydrochloric acid accessibility, peel off conservation rate with embodiment 1.The result is shown in table 2.
Though be not shown in table 1, the roughening treatment face of the whole Copper Foils that use at embodiment, comparative example carries out the plating processing with Ni, Zr and Cr.
In the table 1,
(b) the high-aspect-ratio number/all bump counts are represented with respect to whole bump counts of measuring, and length-width ratio (H/L) is in 1.5～5 scope and the rising height ratio in the projection quantity of the scope of 1～3 μ m.
(c) the close clearance number between projection/all bump counts are represented with respect to whole bump counts of measuring, between the thrust of adjacency the degree of depth be between the above and abutment lug thing of 0.5 μ m distance in the ratio of the quantity in the gap of 0.001～1 mu m range.
In addition, (d) expansion bump count/all bump count is with respect to whole bump counts of measuring, has the ratio of the shape for lugs quantity wideer than root width L.
In addition, (e) projection mean breadth 1 μ m above/all bump counts be with respect to whole bump counts of measuring, the mean breadth of projection is the ratio of the projection quantity more than the 1 μ m.
Should explain, in Fig. 2 with reference to property the photo in the Copper Foil cross section of using is shown among the embodiment 1, the photo in the Copper Foil cross section of use in the comparative example 2 is shown with reference to property ground in Fig. 3.Wherein, the Copper Foil that uses among the embodiment 2 and 3, the trickle alligatoring shape and the Fig. 2 on the surface of the Copper Foil that Rz is different are similar; The Copper Foil that uses in the comparative example 1, the trickle alligatoring shape and the Fig. 3 on the surface of the Copper Foil that Rz is different are similar.
[table 1]
[table 2]
For the copper-clad laminated board that obtains among the embodiment 1,2,3, can confirm that the variable color of the circuit end after the salt acid treatment is below the 200 μ m, the peel strength conservation rate is more than 70%.On the other hand, in the comparative example 1,2, integral body can be confirmed to peel off the variable color that causes because of circuit in the circuit end, and the peel strength conservation rate is lower than 70%.
Can confirm like this, the flexible copper-clad laminated plate that obtains in the present invention since can suppress after the salt acid treatment infiltration, do not produce circuit and peel off, so be the high material of reliability.
Claims (6)
1. metal-clad; It is characterized in that; Single face or two sides at polyimide layer have metal forming; The glass transition temperature of the polyimide layer (i) that joins with said metal forming is more than 300 ℃, and the roughening treatment face that joins with polyimide layer of said metal forming satisfies following condition (a)～(c)
(a) the surface roughness Rz of roughening treatment face is in the scope of 0.5～4 μ m,
(b) skin section of roughening treatment face is the micro crowning shape that is formed by a plurality of alligatoring particles; The length-width ratio H/L that representes with the rising height H of 1 thrust of said micro crowning shape and the ratio of root width L is 50% below in the ratio of the shape for lugs of 1～3 mu m range with respect to the quantity of whole shape for lugs at 1.5～5 scopes and rising height
(c) be that the exist ratio of distance in the gap of 0.001～1 mu m range is below 50% of whole shape for lugs numbers more than the 0.5 μ m and between the abutment lug thing in the degree of depth between the thrust of adjacency.
2. metal-clad according to claim 1, wherein, in claim 1 (b) in the shape for lugs of regulation, having the ratio of the shape for lugs of the width bigger than root width L is below 20% towards zenith directions with respect to the quantity of whole shape for lugs.
3. metal-clad according to claim 1 and 2, wherein, the mean breadth of the shape for lugs that height 1 μ m is above is that the ratio that the above shape for lugs of 1 μ m accounts for whole shape for lugs is more than 10%.
4. according to each described metal-clad in the claim 1～3, wherein, roughening treatment face carries out plating with Ni, Zn and Cr to be handled, and Ni content is 0.1mg/dm
2More than, and the Y value of utilizing luminance meter to measure is that brightness is more than 25.
5. according to each described metal-clad in the claim 1～4; Wherein, Polyimide layer is made up of multilayer, and the polyimide layer glass transition temperature (ii) that does not join with metal forming is higher more than 50 ℃ than the glass transition temperature of polyimide layer (i).
6. according to each described metal-clad in the claim 1～5, wherein, polyimide resin layer and the metal forming initial stage bonding force under the 1mm width is more than the 1.0kN/m, and the peel strength conservation rate of dipping after 1 hour is more than 80% in hydrochloric acid.
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| JP2011-080333 | 2011-03-31 | ||
| JP2011080333A JP5698585B2 (en) | 2011-03-31 | 2011-03-31 | Metal-clad laminate |
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| CN102740613B CN102740613B (en) | 2016-09-14 |
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| JP (1) | JP5698585B2 (en) |
| KR (1) | KR101965174B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114007832A (en) * | 2019-06-17 | 2022-02-01 | 株式会社可乐丽 | Method for manufacturing metal-clad laminate |
| CN114953640A (en) * | 2022-05-27 | 2022-08-30 | 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 |
Families Citing this family (2)
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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 |
| WO2019021895A1 (en) * | 2017-07-24 | 2019-01-31 | 古河電気工業株式会社 | Surface-treated copper foil, and copper-clad laminate sheet and printed wiring board using same |
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| TWI300744B (en) | 2001-04-19 | 2008-09-11 | Nippon Steel Chemical Co | |
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| 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 |
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- 2011-03-31 JP JP2011080333A patent/JP5698585B2/en active Active
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- 2012-03-13 TW TW101108417A patent/TWI528872B/en active
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| JP2005219379A (en) * | 2004-02-06 | 2005-08-18 | Furukawa Circuit Foil Kk | Composite material for substrates and circuit board using it |
| JP2010157571A (en) * | 2008-12-26 | 2010-07-15 | Nippon Steel Chem Co Ltd | Laminated body for flexible wiring board |
| WO2011010540A1 (en) * | 2009-07-24 | 2011-01-27 | 三菱瓦斯化学株式会社 | Resin composite electrolytic copper foil, copper-clad laminate, and printed wiring board |
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| CN114007832A (en) * | 2019-06-17 | 2022-02-01 | 株式会社可乐丽 | Method for manufacturing metal-clad laminate |
| CN114007832B (en) * | 2019-06-17 | 2024-04-19 | 株式会社可乐丽 | Method for producing metal-clad laminate |
| CN114953640A (en) * | 2022-05-27 | 2022-08-30 | 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 |
| 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 | Publication date |
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| KR101965174B1 (en) | 2019-04-03 |
| TWI528872B (en) | 2016-04-01 |
| KR20120112216A (en) | 2012-10-11 |
| JP5698585B2 (en) | 2015-04-08 |
| JP2012213902A (en) | 2012-11-08 |
| CN102740613B (en) | 2016-09-14 |
| TW201251535A (en) | 2012-12-16 |
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