WO2013144992A1 - Stratifié plaqué cuivre ayant une couche de primaire et tableau de connexions l'utilisant - Google Patents

Stratifié plaqué cuivre ayant une couche de primaire et tableau de connexions l'utilisant Download PDF

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Publication number
WO2013144992A1
WO2013144992A1 PCT/JP2012/002063 JP2012002063W WO2013144992A1 WO 2013144992 A1 WO2013144992 A1 WO 2013144992A1 JP 2012002063 W JP2012002063 W JP 2012002063W WO 2013144992 A1 WO2013144992 A1 WO 2013144992A1
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WIPO (PCT)
Prior art keywords
layer
copper
polyimide
clad laminate
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2012/002063
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English (en)
Japanese (ja)
Inventor
岡野　朋樹
田中　竜太朗
内田　誠
辻　誠
成生 林本
健二 関根
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JX Nippon Mining and Metals Corp
Nippon Kayaku Co Ltd
Original Assignee
JX Nippon Mining and Metals Corp
Nippon Kayaku Co Ltd
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Priority to PCT/JP2012/002063 priority Critical patent/WO2013144992A1/fr
Publication of WO2013144992A1 publication Critical patent/WO2013144992A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • 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
    • 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
    • B32B27/28—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive

Definitions

  • the present invention provides a flexible print having a coating layer composed of a Ni layer and a Cr layer on a non-roughened copper foil base surface, a polyimide resin primer layer thereon, and a polyimide layer for insulation thereon.
  • the present invention relates to a copper-clad laminate used for wiring boards and the like.
  • Typical uses of the polyimide resin film include single-sided or double-sided flexible laminates bonded with metal foils typified by copper foils, coverlays for flexible printed wiring boards, and interlayer insulation films for multilayer boards.
  • a laminated board called a two-layer CCL in which a polyimide resin and a metal foil are directly bonded without using an adhesive layer is excellent in terms of miniaturization of wiring and heat resistance of the substrate. Insufficient adhesion is a problem.
  • a manufacturing method of the two-layer CCL a casting method in which a polyimide resin precursor applied on a metal foil is imidized by heating is currently mainstream.
  • a laminating method in which a polyimide film and a metal foil are thermocompression bonded via a thermoplastic polyimide as an adhesive layer
  • a sputtering method in which a metal foil is plated on a sputtered layer provided on the surface of the polyimide film, and the like.
  • copper foils having irregularities formed on the surface by applying a roughening process such as attaching fine copper particles to one side of the copper foil have been used.
  • the anchor effect is obtained by embedding the resin in the uneven shape on the surface of the copper foil, so that the adhesion between the copper foil and the polyimide resin can be improved.
  • the surface of the roughened copper foil is usually coated with an amine compound, a long-chain alkyl compound, or a silicone compound as a rust preventive agent as a surface treating agent, these are removed from the surface of the copper foil.
  • the polyimide resin precursor is applied by a casting method without removing, the peel strength between the obtained two-layer CCL copper foil and the polyimide resin layer is lowered.
  • These surface treatment agents can be removed through complicated steps such as a degreasing step and soft etching, but the surface of the copper foil from which the surface treatment agent has been removed is corroded and oxidized by exposure to air or a polyimide resin precursor. The problem was that it was easy.
  • thermoplastic polyimide varnish is applied to the surface of a non-thermoplastic polyimide film for the purpose of improving the adhesion between the copper foil and the non-thermoplastic polyimide film that is a base resin.
  • a laminating method in which a polyimide layer is formed and then thermocompression bonded with a copper foil is disclosed.
  • those that satisfy all of the peel strength at normal temperature, the peel strength after exposure to high temperature conditions, and the peel strength after exposure to wet heat conditions have not been obtained.
  • the laminating method using the varnish tends to deteriorate the dimensional stability.
  • Patent Document 2 discloses a method of providing a Ni layer and / or a Cr layer on the surface of a roughened or non-roughened copper foil in order to improve adhesion to a polyimide resin. Specifically, a Ni layer is formed on the copper foil surface by Ni plating, and / or a Cr layer is formed by a plating method or chromate treatment, and a polyamic acid varnish is applied thereon, dried, imidized, and a polyimide layer A copper-clad laminate having the structure is disclosed.
  • Patent Document 3 discloses a primer layer resin composition containing an epoxy resin and a specific ring-closing polyimide for the purpose of improving the adhesion between the non-roughened copper foil and the polyimide resin (insulating resin layer). Has been.
  • the copper foil roughening treatment step can be omitted, and production costs can be significantly reduced. Further, since it is not necessary to provide an overetching time for dissolving the roughened portion in circuit etching, the total etching cost can be reduced.
  • the printed wiring board can be thinned, and the resin that has penetrated into the uneven portion does not remain as an etching residue, so that a finer wiring pattern can be formed. Furthermore, since the electrical resistance on the surface of the wiring is reduced, particularly when a high-frequency current is used, the current density on the surface of the copper foil is increased due to the skin effect, so that the characteristics of the printed wiring board can be improved.
  • the present invention is a copper-clad laminate for a flexible printed wiring board obtained by a casting method without roughening the copper foil, and has good adhesion between the copper foil and the polyimide resin as the base resin. It aims at providing the copper clad laminated board which has a rust prevention effect of copper foil while having it.
  • the present invention further provides, in a preferred embodiment, a copper-clad laminate that is free from foaming due to residual solvent and the like during the production of the copper-clad laminate and has reduced curling after etching. For the purpose.
  • the present inventors have formed a Ni layer and a Cr layer (coating layer) that are extremely thin and have a uniform thickness on a copper foil, and a polyimide having a specific structure as a primer resin.
  • the present inventors have found that the above problems can be solved by using a resin, and have completed the present invention.
  • a copper-clad laminate that satisfies the following requirements: (1) The coating layer is composed of a Ni layer and a Cr layer laminated in order from the copper foil surface, (2) The coating amounts of Ni and Cr in the coating layer are 15 to 440 ⁇ g / dm 2 and 15 to 210 ⁇ g / dm 2 , respectively.
  • Solvent-soluble polyimide is an aromatic tetrabasic acid dianhydride described in the following (i) or (ii) and an aromatic diamine described in the following (iii) or (iv) (i) The following formula (1)
  • oxydiphthalic dianhydride represented by (Ii) both at least one of the oxydiphthalic dianhydride and other aromatic tetrabasic dianhydrides; (Iii) The following formula (2)
  • At least one aromatic diamine other than the formula (2) is 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 3,3 ′.
  • the copper clad laminate according to 1 above which is at least one diaminodiphenol selected from the group consisting of fluorene. 3.
  • the tetrabasic dianhydride used in the above reaction is (I) oxydiphthalic dianhydride of formula (1) alone or (Ii) Oxydiphthalic dianhydride of formula (1) and the following formula (3)
  • R 4 represents a methyl group
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or a trifluoromethyl group.
  • R 4 represents a methyl group
  • R 5 represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or a trifluoromethyl group.
  • the polyimide layer (D) directly bonded to the primer resin (B) layer is a polyimide layer (D) obtained by imidizing a polyimide resin precursor (C) layer containing a corresponding polyamic acid by heating. 5.
  • the primer resin (B) layer is obtained by applying and drying a resin varnish containing the primer resin (B) on the surface of the coating layer provided on the copper foil (A), and the primer resin ( B)
  • Resin varnish containing primer resin (B) is solvent-soluble polyimide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, ⁇ -butyrolactone, cyclopentanone And a copper-clad laminate according to 6 above, which is a resin varnish dissolved in at least one solvent selected from the group consisting of methyl benzoate. 8).
  • Polyimide resin precursor (C) layer containing polyamic acid is represented by the following formula (7)
  • R 6 represents a tetravalent aromatic group
  • R 7 represents a divalent aromatic group
  • x represents a real number of 1 or more in terms of the average number of repetitions.
  • R 8 represents a tetravalent aromatic group
  • R 9 represents a hydrogen atom or a C1-C3 alkyl group.
  • the copper-clad laminate of the present invention has high adhesion (peel strength) between the unroughened copper foil and the polyimide layer (D), and is further subjected to severe high temperature and high humidity conditions. In addition, high adhesion is maintained and solder heat resistance is excellent.
  • This effect was achieved by forming the Ni layer and the Cr layer to be thin and uniform in thickness and using the primer resin (B) layer made of polyimide containing a specific component. The effect is that the arrangement period of the metal atoms of the Ni layer and the Cr layer constituting the coating layer, the flexible ether bond of the primer resin (B) and the appropriate repetition length of the imide group are matched, and the primer resin (B ) Layer is believed to be obtained by showing high adhesion to the coating layer.
  • the copper clad laminated board of this invention has an effect as a rust prevention process layer of copper foil (A) by having said primer resin (B) layer.
  • the copper clad laminate of the present invention is obtained by applying a polyimide resin precursor (C) varnish containing polyamic acid, and then imidizing the resulting layer (polyimide resin precursor (C) layer).
  • C polyimide resin precursor
  • the primer resin (B) appropriately includes a structure having high rigidity and stacking properties in addition to an ether bond, curling after etching is not accompanied by an increase in linear expansion coefficient. It is suppressed. Therefore, the copper clad laminate of the present invention is practical and extremely useful in the field of electrical and electronic materials.
  • the copper foil (A) provided with a coating layer and not subjected to the roughening treatment has a surface roughness (Rz) of 2 ⁇ m or less.
  • Rz surface roughness
  • the coating amount of the coating layer is usually in the range of 15 to 440 ⁇ g / dm 2 for Ni and in the range of 15 to 210 ⁇ g / dm 2 for Cr.
  • the maximum thickness of the coating layer is usually 0.5 to 5 nm, and the minimum value is usually 80% or more of the maximum value. If the coating amount, the thickness of the coating layer, and the uniformity of the thickness of the coating layer (minimum thickness is 80% or more of the maximum value) are greatly impaired, adhesion with the polyimide (B) layer, etching property, Properties such as flexibility and the antioxidant effect of the copper foil are reduced. Particularly in the present invention, the uniformity of the thickness of the coating layer is important for obtaining the characteristics of the present invention.
  • the Ni coating amount is preferably about 15 to less than 300 ⁇ g / dm 2 , preferably about 20 to 200 ⁇ g / dm 2 , more preferably about 40 to 180 ⁇ g / dm 2 .
  • the coating amount of Cr is preferably 15 to less than 180 ⁇ g / dm 2 , preferably about 20 to 150 ⁇ g / dm 2 , more preferably about 30 to 100 ⁇ g / dm 2 .
  • the Ni coating amount and the Cr coating amount are not limited as long as they are within the above ranges.
  • the Cr coating amount is more than 0.5 parts by mass, preferably 1 part by mass or less, more preferably 0.6 to 1 part by mass.
  • the maximum value of the thickness of the coating layer is preferably about 0.5 to 4 nm, more preferably about 1 to 4 nm. In some cases, about 1.5 to 4 nm is most preferable.
  • the thickness of a coating layer can be measured by observing the cross section of a coating layer visually using a transmission electron microscope.
  • the coating layer composed of the Ni layer and the Cr layer is preferably formed by a sputtering method.
  • a sputtering apparatus is usually used to form the Ni layer and the Cr layer by sputtering.
  • the sputtering apparatus may be any commercially available apparatus as long as it can form the above-described coating layer.
  • a uniform thickness the minimum value of the thickness of the coating layer is 80% of the maximum value. It is difficult to form the above-mentioned coating layer, and specific adhesion with the primer resin cannot be obtained.
  • the solvent-soluble polyimide used as the primer resin (B) in the present invention is a tetrabasic acid dianhydride containing at least the oxydiphthalic acid dianhydride represented by the formula (1), and at least the formula (2).
  • the polyamic acid obtained by addition reaction with the diamine containing bis (aminophenoxy) benzene represented can be obtained by further dehydrating and ring-closing.
  • the oxydiphthalic dianhydride represented by the formula (1) is specifically described, the following formula (9)
  • the solvent-soluble polyimide used as the primer resin (B) in the present invention has a number average molecular weight of 1,000 to 50,000 and a weight average molecular weight of 5,000 to 500,000. Ring-closed polyimide.
  • the series of reactions of polyamic acid synthesis by addition reaction of the above-mentioned tetrabasic dianhydride and diamine and subsequent polyimide formation by dehydration ring closure is preferably performed in one pot.
  • the amount of the diamine used in the addition reaction is usually 0.5 to 2.0 equivalents, preferably 0.5 to 2.0 equivalents, preferably 1 to 20 equivalents of the amino group of the diamine with respect to 1 equivalent of the acid anhydride group of the tetrabasic dianhydride used.
  • the amount is 0.8 to 1.2 equivalents, more preferably 0.9 to 1.1 equivalents.
  • the diamine used at both ends is bonded to obtain a polyimide having a terminal amino group
  • the diamine used at both ends is bonded to obtain a polyimide having a terminal amino group
  • an excess of tetrabasic acid dianhydride is used.
  • the acid anhydride used at both ends is bonded to obtain a polyimide having a terminal acid anhydride group.
  • a polyimide having random amino groups and acid anhydride groups at the ends can be obtained.
  • the number average molecular weight and the weight average molecular weight are too small, the heat resistance and mechanical strength inherent to the polyimide are hardly expressed, and the surface of the coating layer provided on the copper foil (A) is the primer resin (B). It becomes susceptible to the influence of the terminal amino group or terminal acid anhydride group therein. Moreover, when the number average molecular weight and the weight average molecular weight are too large, it becomes difficult to form a thin film of the primer layer due to an increase in viscosity when used as a solution, and adhesion between the coating layer and the primer layer Sex is reduced.
  • the “solvent-soluble polyimide” in the present invention is a polyimide that provides a solution having a concentration of at least 5% by mass, preferably 10% by mass when dissolved in an organic solvent.
  • the number and weight average molecular weight indicate molecular weights calculated in terms of polystyrene based on the measurement results of gel permeation chromatography.
  • the solvent-soluble polyimide used as the primer resin (B) in the present invention may be one in which the oxydiphthalic anhydride of the above formula (1) is used alone as the tetrabasic acid dianhydride component.
  • An aromatic tetrabasic acid dianhydride may be used in combination, and the diamine component may be a bis (aminophenoxy) benzene of the formula (2) used alone, It may be a combination of other aromatic diamines.
  • the solvent-soluble polyimide preferably contains at least 30 mol% or more of the oxydiphthalic anhydride-derived component of the formula (1) with respect to the total amount of the tetrabasic dianhydride-derived component contained therein.
  • the solvent-soluble polyimide preferably contains at least 3 to 100 mol% of the bis (aminophenoxy) benzene-derived component of the formula (2) with respect to the total amount of the diamine-derived component contained therein. Is from 4 to 100 mol%, more preferably from 5 to 100 mol%, most preferably from 5 to 60 mol%, and the balance being other aromatic diamines.
  • the calculated value of the hydroxyl group equivalent of the primer resin (B) is usually 3,000 g / eq. Hereinafter, preferably 2,000 g / eq.
  • the following amounts are used: Since the effect of suppressing foaming varies depending on the type of the polyimide resin precursor (C) described later, it is not necessarily limited to this range.
  • the hydroxyl equivalent may be zero.
  • a preferable range is 500 to 2000 g / eq. Degree, more preferably 1000 to 2000 g / eq. You can list the degree.
  • the amount of these diaminodiphenols used is about 2 to 40 mol%, preferably about 10 to 30 mol%, based on the total amount of diamine used in the addition reaction.
  • the balance is bis (aminophenoxy) benzene of the above formula (2) or other aromatic diamine.
  • the polyimide resin precursor (C) is imidized by using, as a primer resin (B), a solvent-soluble polyimide obtained by using these diaminodiphenols together with the bis (aminophenoxy) benzene of the formula (2).
  • the solvent-soluble polyimide is one of the preferred primer resins (B).
  • a methyl or trifluoromethyl group is formed on each benzene ring together with the bis (aminophenoxy) benzene of the formula (2) in the addition reaction.
  • the primer resin (B) as the tetrabasic acid dianhydride, together with the oxydiphthalic anhydride of the formula (1), biphenyltetracarboxylic dianhydride or pyromellitic dianhydride
  • the copper-clad laminate of the present invention using a solvent-soluble polyimide obtained by using the product as a primer resin (B) is also preferable. Also in this case, a copper-clad laminate having a small curl after etching is obtained.
  • the bis (aminophenoxy) benzene represented by the formula (2) is used to reduce the linear expansion coefficient of the primer resin (B) and to obtain a copper-clad laminate having a small curl after etching of the copper-clad laminate.
  • R 4 represents a methyl group
  • R 5 represents a functional group selected from a hydrogen atom, a methyl group, an ethyl group, a methoxy group, and a trifluoromethyl group, as described above.
  • the amount of these aromatic diamines used is 0 to 95 mol%, usually 10 mol% or more, preferably 15 to 95 mol%, more preferably 25 to 85 mol%, based on the total mol of diamine used in the addition reaction. Mol%. If the amount of these aromatic diamine components used is too small, the curl suppression effect may not be obtained.
  • the above formula is used together with the oxydiphthalic anhydride of formula (1) as a tetracarboxylic dianhydride during the addition reaction.
  • the tetracarboxylic dianhydride (pyromellitic dianhydride or biphenyltetracarboxylic dianhydride) described in (11) may be used in combination.
  • the amount of tetracarboxylic dianhydride used in combination is 0 to 70 mol%, usually 20 to 70 mol%, preferably 30 to 60 mol%, based on the total mol of the acid dianhydride used in the addition reaction. .
  • the balance is usually oxydiphthalic anhydride of the above formula (1).
  • other aromatic tetracarboxylic dianhydrides may be used in combination as long as the present invention is not hindered.
  • tetrabasic acid dianhydrides and diamines other than the above aromatic tetrabasic acid dianhydrides and aromatic diamines can be used in combination as long as they do not hinder the present invention.
  • the amount of these other diamines used is not particularly limited as long as it does not hinder the present invention, but is usually 0 to 50 mol%, preferably 0 to 40 mol%, based on the total mol of diamines used in the addition reaction. It is.
  • Examples of the tetrabasic acid dianhydride other than the tetrabasic acid dianhydride of the formula (1) and the tetrabasic acid dianhydride described in the formula (11) include ethylene glycol-bis (anhydrotrimellitate), Glycerin-bis (anhydrotrimellitate) monoacetate, 1,2,3,4, -butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-anhydrodicarboxyphenyl) propane, 2,2-bis (3,4-anhydrodicarboxyphenyl) ) Hexafluoropropane, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methylcyclohexene-1,2-dicarboxylic anhydr
  • the amount of these other tetrabasic acid dianhydrides used is not particularly limited as long as it does not hinder the present invention, but is usually 0 to 50 mol% with respect to the total mol of acid dianhydrides used for the addition reaction, Preferably, it is 0 to 40 mol%.
  • aromatic tetracarboxylic dianhydride (I) oxydiphthalic dianhydride of formula (1), or (Ii) At least one selected from the group consisting of oxydiphthalic dianhydride of formula (1) and biphenyltetracarboxylic dianhydride and pyromellitic dianhydride represented by formula (3) (preferably Is biphenyltetracarboxylic dianhydride)
  • aromatic diamine (Iii) both bis (aminophenoxy) benzene of formula (2) and at least one selected from the group consisting of aromatic diamines described in formula (4), Is a combination using Further, the above (i) or (ii) is used as the aromatic tetracarboxylic dianhydride, and (i) bis (aminophenoxy
  • the primer resin (B) layer in the present invention is formed by applying a resin varnish containing a solvent-soluble polyimide dissolved in a solvent to the surface of the coating layer provided on the copper foil (A) and drying it.
  • concentration of the resin solid content in the resin varnish may be a viscosity suitable for application of the resin varnish, and varies depending on the solvent-soluble polyimide used, but is usually 5 to 50% by mass in the solvent, preferably 10%. ⁇ 40% by weight.
  • the reaction solution can be used as it is as a resin varnish. If necessary, the resin varnish may be concentrated or further diluted by adding a solvent.
  • the addition reaction and the dehydration ring closure reaction are preferably carried out in a solvent capable of dissolving both the polyamic acid as an intermediate and the ring-solvated solvent-soluble polyimide (primer resin (B)).
  • solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, ⁇ -butyrolactone, cyclopentanone and methyl benzoate.
  • the addition reaction it is also preferable to add a small amount of pyridine as a catalyst.
  • a small amount of a nonpolar solvent having a relatively low boiling point such as toluene, xylene, hexane, cyclohexane or heptane is added as a dehydrating agent, and water produced as a by-product during the reaction is removed from the reaction system. It is preferable to carry out the dehydration reaction.
  • the reaction temperature during the addition reaction and dehydration ring-closing reaction is usually 150 to 220 ° C., preferably 180 to 200 ° C., and the reaction time is usually 2 to 10 hours, preferably 5 to 8 hours.
  • the addition amount of the catalyst is usually 0.1 to 5% by mass with respect to the reaction solution, and the addition amount of the dehydrating agent is usually 5 to 20% by mass with respect to the reaction solution.
  • the primer resin (B) of the present invention is a solvent-soluble polyimide
  • the resin varnish in which the primer resin is dissolved is applied to the surface of the coating layer provided on the copper foil (A), and then at a low processing temperature.
  • the primer resin (B) layer can be formed simply by drying the solvent. Therefore, in the present invention, the primer resin (B) layer made of polyimide can be easily formed.
  • additives may be added to the primer resin (B) of the present invention as long as the adhesive strength to the coating layer and the polyimide layer (D) provided on the copper foil (A) is not impaired. it can.
  • the additives include organic additives such as aromatic polyamide resins, epoxy resins and phenol resins, inorganic additives such as silica compounds, pigments, dyes, antihalation agents, brightening agents, surfactants, and leveling. Agents, plasticizers, flame retardants, antioxidants, fillers, antistatic agents, viscosity modifiers, accelerators, light stabilizers, photocatalysts, low dielectric materials, conductors, magnetic materials, and thermally decomposable compounds. It is done.
  • the primer resin (B) layer is formed on the surface of the coating layer provided on the copper foil (A) not subjected to the roughening treatment so that the thickness after drying becomes 1 to 5 ⁇ m. It is obtained by applying and drying a resin varnish containing). For example, a resin varnish containing 20% by mass of the primer resin (B) is applied on the coating layer so as to have a thickness of 15 ⁇ m, and is usually 5 to 60 minutes at 80 to 200 ° C., preferably 10 to 130 to 150 ° C. By drying for ⁇ 30 minutes, a primer layer with a thickness of approximately 3 ⁇ m is obtained.
  • the heat source during drying may be hot air or a far-infrared heater, but it is preferable to use hot air and a far-infrared heater in combination in order to prevent the vaporized solvent from staying and to heat the inside of the resin.
  • the polyimide layer (D) that directly adheres to the primer resin (B) layer is usually obtained by imidizing the polyimide resin precursor (C) layer containing polyamic acid formed on the primer resin (B) layer. be able to. Moreover, it is preferable to form a polyimide resin precursor (C) layer by the normal casting method.
  • the polyimide resin precursor (C) layer comprises a tetracarboxylic dianhydride and a diamine, usually an aromatic tetracarboxylic dianhydride and an aromatic diamine, and a solvent that dissolves polyamic acid, such as N-methyl-2-pyrrolidone.
  • a reaction solution containing polyamic acid obtained by reacting in a polar solvent such as N, N-dimethylacetamide is used as a resin varnish by adjusting the resin concentration as necessary, on the primer resin (B) layer. It can be obtained by applying and drying.
  • the obtained polyimide resin precursor (C) layer is directly bonded to the primer resin (B) layer by dehydrating and ring-closing, for example, under conditions of 250 to 400 ° C. for 0.5 to 20 hours, and forming a polyimide. It can be set as the copper clad laminated board of this invention which has a polyimide layer (D).
  • the polyimide layer (D) directly adhered to the primer resin (B) layer is a polyimide layer used for a conventional copper clad laminate called a two-layer CCL, there is no particular problem.
  • the polyimide layer (D) on the primer resin (B) layer of the copper-clad laminate of the present invention is formed by heating and ring-closing the polyimide resin precursor (C) layer containing polyamic acid and the polyimide layer (D). It is preferable to do this. Any polyimide resin precursor (C) layer may be used as long as it contains polyamic acid and can be formed into a polyimide layer (D) by heat ring closure.
  • the polyimide resin precursor (C) layer may be obtained by applying and drying a resin varnish containing only polyamic acid as a resin component, or the following formula (7) of both terminal amino groups:
  • R 6 represents a tetravalent aromatic residue
  • R 7 represents a divalent aromatic diamine residue
  • x represents a real number of 1 or more in terms of average number of repetitions.
  • a polyamic acid having an amino group at the terminal represented by the following formula (8) (Wherein R 8 represents a tetravalent aromatic group, and R 9 represents a hydrogen atom or a C1-C3 alkyl group.) It may be obtained by applying and drying a resin varnish containing a compound represented by: In the present invention, the latter is preferred.
  • the polyimide resin precursor (C) layer obtained preferably contains a polyamic acid having an amino group at the terminal represented by the above formula (7) and a compound represented by the formula (8).
  • the polyamic acid content in the polyimide resin precursor (C) layer is preferably from 80 to 100% by mass, more preferably from 90 to 99% by mass, and the remaining tetracarboxylic dianhydride is added to water or It may contain a tetracarboxylic acid produced by addition ring-opening of C1-C3 alcohol and / or its ester.
  • a polyamic acid is a compound represented by Formula (7)
  • it is preferable that the polyimide resin precursor (C) layer contains the compound represented by Formula (8).
  • the polyamic acid content in the polyimide resin precursor (C) layer is preferably 80 to 100% by mass, more preferably 90 to 99% by mass.
  • the balance is the compound represented by the formula (8), and a trace amount solvent or the like may be included.
  • the tetravalent aromatic group of R 6 in formula (7) and the tetravalent aromatic group of R 8 may be the same or different, but the same is usually preferred.
  • the resin varnish a known polyamic acid resin varnish for a copper clad laminate or a commercially available polyamic acid resin varnish can be used. Examples of commercially available products of the latter polyamic acid resin varnish include KAYAFLEX KPI-126 (manufactured by Nippon Kayaku Co., Ltd.).
  • the adhesive strength at the interface is displayed in a normal (at a temperature of about 25 ° C.) atmosphere, as well as after being held at a high temperature of about 150 ° C., for example, for 168 hours or at 40 ° C. and a humidity of 95% (95% RH) ), Etc., for example, even after holding for 96 hours, it is practically preferably 0.8 N / mm or more, more preferably 1.0 N / mm or more.
  • the wiring board for a flexible printed board of the present invention can be obtained by subjecting the copper-clad laminate of the present invention to processing such as punching, etching, drilling and plating.
  • Preferred examples of the copper clad laminate of the present invention include the following.
  • the amount of the oxydiphthalic anhydride-derived component represented by the formula (1) is 30 mol% or more, preferably 40 to 100 mol%, with respect to the total amount of the tetrabasic acid dianhydride-derived component in the solvent-soluble polyimide, and the balance Are components derived from other aromatic tetrabasic dianhydrides
  • the bis (aminophenoxy) benzene-derived component represented by the formula (2) is 3 to 100 mol%, preferably 4 to 100 mol%, more preferably 5 to the total amount of the diamine-derived component in the solvent-soluble polyimide.
  • Copper-clad laminate (III) The copper-clad laminate according to (II), wherein the diaminodiphenol is the diaminodihydroxybiphenyl.
  • IV The copper clad laminate according to the above (II), wherein the diaminodiphenol is 3,3′-diamino-4,4′-dihydroxybiphenyl.
  • the solvent-soluble polyimide is at least 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) as the other aromatic diamine. ) Obtained by using in combination at least one selected from the group consisting of biphenyl, 4,4′-diamino-2′-methoxybenzanilide and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide.
  • At least one of the other aromatic diamines described in (VII) above is 4,4′-diamino-2,2′-dimethylbiphenyl or 3,7-diamino-2,8-dimethyldibenzothiophene.
  • the copper clad laminate according to (VII) above which is 5,5-dioxide, more preferably 4,4′-diamino-2,2′-dimethylbiphenyl.
  • IX Any one of the above (VI) to (VIII), wherein the amount of the other aromatic diamine used is 0 to 96 mol%, preferably 40 to 95 mol%, based on the total amount of the aromatic diamine.
  • the solvent-soluble polyimide is a tetrabasic dianhydride, together with an oxydiphthalic anhydride represented by the formula (1), a biphenyltetracarboxylic dianhydride represented by the formula (3) and a pyro
  • polyimide layer (D) is a polyimide layer (D) obtained by imidizing a polyimide resin precursor (C) layer containing a corresponding polyamic acid by heating.
  • a polyimide resin precursor (C) layer containing a polyamic acid contains 80 to 100% by mass of polyamic acid and contains 0 to 20% by mass of a tetracarboxylic acid derivative represented by the formula (8).
  • (XX) Normal state of a copper foil (A) having a coating layer satisfying the above conditions (1) to (3) and not subjected to the roughening treatment, and a primer resin (B) layer directly adhered to the coating layer
  • (XXI) The copper clad laminate according to (XX), wherein the normal peel strength is 1.0 N / mm or more.
  • Production Example 1 (Production of copper foil (A) having a coating layer used in the present invention)
  • a non-roughened rolled copper foil (C1100 manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 18 ⁇ m, surface roughness (Rz) 0.7 ⁇ m) is used, and this copper foil is attached in advance from one side
  • a Ni layer and a Cr layer were sequentially formed by a continuous sputtering apparatus so as to have a thickness of 1 nm.
  • the respective coating amounts of Ni and Cr were Ni: 85 ⁇ g / dm 2 and Cr: 70 ⁇ g / dm 2 .
  • the maximum value of the thickness of the coating layer including the Ni layer and the Cr layer was 2.1 nm, and the minimum value was 1.9 nm (ratio of the minimum value to the maximum value: about 90%).
  • This obtained copper foil is designated as A-1.
  • TEM measurement conditions and equipment TEM (manufactured by Hitachi, Ltd., model H9000NAR) ⁇ Accelerating voltage: 300kV ⁇ Magnification: 300,000 times ⁇ Observation field: 60 nm ⁇ 60 nm
  • Production Example 2 (Production of Comparative Copper Foil with Coating Layer Formed by Plating Method)
  • a copper foil base material a non-roughened rolled copper foil (C1100 manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 18 ⁇ m, surface roughness (Rz) 0.7 ⁇ m) is used, and an example of production from one side of this copper foil
  • Ni electroplating and chromate treatment are sequentially performed so that the Ni layer and the Cr layer have an average thickness of about 1 nm, respectively. did.
  • Ni plating / plating bath nickel sulfamate (110 g / L as Ni 2+ ), H 3 BO 3 (40 g / L) -Current density: 1.0 A / dm 2 ⁇ Bath temperature: 55 °C Ni content: 95 ⁇ g / dm 2 (thickness approximately 1.1 nm)
  • Chromate treatment / Plating bath CrO 3 (1 g / L), Zn (powder 0.4 g), Na 2 SO 4 (10 g / L) -Current density: 2.0 A / dm 2 ⁇ Bath temperature: 55 °C -Cr amount: 70 ⁇ g / dm 2 (Cr amount almost the same as in Production Example 1)
  • Synthesis example 1 APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound is added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirrer.
  • Benzene manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 51.49 g (0.176 mol), 79.65 g of N-methyl-2-pyrrolidone as a solvent were charged and stirred at 70 ° C. for 30 minutes while flowing dry nitrogen. .
  • the reaction liquid cooled to 80 ° C. or lower is subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 ⁇ m, whereby a primer resin varnish containing 34% by mass of polyimide (hereinafter referred to as B-1). ) was obtained.
  • the number average molecular weight of the primer resin was 9,900, and the weight average molecular weight was 54,000 (all were calculated in terms of polystyrene based on the measurement results of gel permeation chromatography. The same applies hereinafter).
  • Synthesis example 2 APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound is added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirrer.
  • Benzene manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 30.02 g (0.103 mol), HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, Nippon Kayaku Co., Ltd., molecular weight 216.
  • a heat ring closure reaction was carried out at 180 ° C. for 3 hours, followed by heating at the same temperature for 2 hours to remove pyridine and toluene.
  • the reaction solution cooled to 80 ° C. or lower was subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 ⁇ m, thereby obtaining a primer resin varnish containing 34% by mass of polyimide (hereinafter referred to as B-2). 200 g) was obtained.
  • the number average molecular weight of the primer resin was 10,500, and the weight average molecular weight was 36,400.
  • the theoretical hydroxyl equivalent calculated from the amount of raw materials charged is 1500 g / eq. Met.
  • Synthesis example 3 APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound is added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirrer.
  • Benzene manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 1.08 g (0.003 mol), m-TBHG (4,4′-diamino-2,2′-dimethylbiphenyl, manufactured by Wakayama Seika Co., Ltd., molecular weight 212.29) 7.04 g (0.033 mol), HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, Nippon Kayaku Co., Ltd., molecular weight 216.24) 1.53 g (0.007) Mol) and 54.68 g of N-methyl-2-pyrrolidone as a solvent were added and stirred at 70 ° C. for 30 minutes while flowing dry nitrogen.
  • ODPA 4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22) 8.02 g (0.026 mol), BPDA (3,3 ′, 4, 4'-biphenyltetracarboxylic dianhydride, manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22) 5.068 g (0.017 mol), N-methyl-2-pyrrolidone 74.14 g as a solvent, pyridine 0. 68 g and 23.70 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C.
  • Synthesis example 4 APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound is added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirrer.
  • Benzene manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 5.14 g (0.018 mol), MODABAN (4,4′-diamino-2′-methoxybenzanilide, manufactured by Nippon Pure Chemicals Co., Ltd., molecular weight 257.29 ) 4.52 g (0.018 mol), HAB (3,3′-diamino-4,4′-dihydroxybiphenyl, Nippon Kayaku Co., Ltd., molecular weight 216.24) 1.64 g (0.008 mol), As a solvent, 45.20 g of N-methyl-2-pyrrolidone was charged and stirred at 70 ° C. for 30 minutes while flowing dry nitrogen.
  • the reaction solution cooled to 80 ° C. or lower was subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 ⁇ m, thereby obtaining a primer resin varnish containing 14% by mass of polyimide (hereinafter referred to as B-4). 120 g) was obtained.
  • the number average molecular weight of the primer resin was 12,900, and the weight average molecular weight was 83,900.
  • the theoretical hydroxyl equivalent calculated from the amount of raw materials charged is 1500 g / eq. Met.
  • Synthesis example 5 APB-N (1,3-bis- (3-aminophenoxy) as a diamine compound is added to a 500 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen inlet and a stirrer.
  • Benzene manufactured by Mitsui Chemicals, Inc., molecular weight 292.33) 0.87 g (0.003 mol)
  • TFMB 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, Toray Fine Chemical Co., Ltd.
  • ODPA 4,4′-oxydiphthalic anhydride, Manac Co., Ltd., molecular weight 310.22
  • BPDA 3,3 ′, 4,
  • tetracarboxylic dianhydride 4′-biphenyltetracarboxylic dianhydride, manufactured by Mitsubishi Chemical Corporation, molecular weight 294.22
  • N-methyl-2-pyrrolidone 79.46 g as a solvent
  • pyridine 0. 57 g of toluene and 26.37 g of toluene as a dehydrating agent were added, and the temperature in the reactor was increased to 180 ° C.
  • a heat ring closure reaction was carried out at 180 ° C. for 3 hours, followed by heating at the same temperature for 2 hours to remove pyridine and toluene.
  • the reaction solution cooled to 80 ° C. or lower was subjected to pressure filtration using a Teflon (registered trademark) filter having a pore size of 3 ⁇ m, thereby obtaining a primer resin varnish containing 12% by mass of polyimide (hereinafter referred to as B-5). 180 g was obtained.
  • the number average molecular weight of the primer resin was 19,600, and the weight average molecular weight was 64,700.
  • the theoretical hydroxyl equivalent calculated from the amount of raw materials charged is 1500 g / eq. Met.
  • a heat ring closure reaction was carried out at 180 ° C. for 3 hours, followed by heating at the same temperature for 2 hours to remove pyridine and toluene.
  • the reaction solution cooled to 80 ° C. or lower was subjected to pressure filtration using a Teflon (registered trademark) filter having a pore diameter of 3 ⁇ m, thereby obtaining a primer resin varnish containing 15% by mass of polyimide (hereinafter referred to as B-6 and 180 g was obtained.
  • the number average molecular weight of the primer resin was 19,600, and the weight average molecular weight was 85,700.
  • the theoretical hydroxyl equivalent calculated from the amount of raw materials charged is 1500 g / eq. Met.
  • Examples 1 to 6 Comparative Examples 1 to 4 As the copper foil (A), the copper foil (A-1) obtained in Preparation Example 1, and as the comparative copper foil, the copper foil (A-2) obtained in Preparation Example 2 and BHY (rolled copper foil, Nikko Metal) Co., Ltd. (hereinafter referred to as (A'-1)) (without surface roughening treatment) and CF-T9FZ-HTE (electrolytic copper foil, manufactured by Fukuda Metal Foil Co., Ltd., hereinafter referred to as (A'-2)
  • the resin varnishes (B-1) to (B-6) obtained in Synthesis Examples 1 to 6 were used as the primer resin (B).
  • the A-1 copper foil is coated on the surface of the coating layer, and the other copper foil is coated on the non-roughened surface so that the film thickness after drying is 2 ⁇ m except for Comparative Example 1.
  • Each resin varnish was applied to each copper foil with an applicator (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The coating film was dried at 130 ° C. for 10 minutes to obtain a copper foil provided with a primer layer.
  • a polyimide resin precursor (C) KAYAFLEX KPI-126 (manufactured by Nippon Kayaku Co., Ltd., a resin varnish containing a polyamic acid resin having amino groups at both ends and a tetracarboxylic acid derivative of the above formula (8)) (this resin (C-1) is used, and Comparative Example 1 is applied directly to the surface of the coating layer of A-1 copper foil and the others on the primer layer by a casting method so that the film thickness after imidization is 25 ⁇ m. The resin varnish was applied. The coating film was dried at 130 ° C. for 10 minutes, and then imidized at 350 ° C. for 2 hours to obtain a copper-clad laminate of the present invention and a copper-clad laminate for a comparative test.
  • a masking tape (trade name Clear Line Tape No. 557, manufactured by Nichiban Co., Ltd.) was formed on the copper foil side surface of the copper clad laminate obtained in Examples 1 to 6 and Comparative Examples 1 to 4. Then, etching was performed in an etching solution heated to 40 ° C. (ferric chloride aqueous solution 45 ° Baume) for 30 minutes, and the masking tape was peeled off to form a 10 mm wide copper foil pattern.
  • etching solution heated to 40 ° C. ferric chloride aqueous solution 45 ° Baume
  • the polyimide resin layer side is attached to the reinforcing plate using a bonding sheet, the end of the 10 mm wide copper foil is peeled off from the polyimide using a cutter knife, and a Tensilon tester (AUTOGRAPH: manufactured by Shimadzu Corporation) is used.
  • the peel strength between the copper foil and the polyimide resin layer in the 90 ° direction was measured, and this was defined as the normal peel strength.
  • a normal state means the state which put the obtained copper clad laminated board in normal temperature (25 degreeC).
  • the peel strength after the laminate was held at 150 ° C. for 168 hours was defined as heat-resistant peel strength
  • the peel strength after retained at 40 ° C. and 95% RH for 96 hours was defined as moisture-heat peel strength.
  • the copper clad laminate of Example 1 using the copper foil (A-1) and the primer resin (B-1) of the present invention has a normal peel strength as compared with Comparative Example 1 having no primer layer. In both cases of heat resistance and moisture heat resistance, it is remarkably high, and is also excellent in terms of rust prevention effect.
  • Comparative Examples 2 and 3 using a copper foil having no Ni, Cr coating layer and Example 2 of the present invention are compared, the present invention is in any case where the peel strength is normal, heat resistance and moisture heat resistance. Is remarkably high, and is also clearly superior in terms of heat resistance.
  • the copper-clad laminate of Example 2 using the copper foil (A-1) is the same primer resin as that of Example 2 on the copper foil (A-2) provided with Ni and Cr coating layers by plating.
  • the peel strength showed the value remarkably high in any case of a normal state, heat resistance, and heat-and-moisture resistance.
  • the peel strength is remarkably higher in any of the normal state, heat resistance, and heat and moisture resistance than any of the comparative examples. Excellent values are also shown in the radius of curvature and the linear expansion coefficient of the primer resin.
  • the polyimide layer (D) is specified on the surface of the coating layer of the copper foil (A-1) having a Ni, Cr coating layer having a very thin uniform thickness provided by sputtering.
  • the copper-clad laminates of the present invention bonded through a primer resin layer (B) made of a solvent-soluble polyimide are all markedly high in both peel strength, heat resistance and moisture heat resistance, and also have heat resistance. It has a high anticorrosive effect, has no foaming in Examples 2 to 6, and has a remarkably excellent curvature radius after etching in Examples 3 to 6, and is extremely useful as a copper clad laminate. It is clear.
  • the copper-clad laminate of the present invention has a peel strength that is remarkably high in any of normal state, heat resistance and moisture heat resistance, high heat resistance such as solder heat resistance, and further has a rust prevention effect.
  • foaming at the time of forming the polyimide resin layer is eliminated, and the curvature radius after etching is increased (warping after etching). Can be reduced). Therefore, it is extremely useful in the field of electrical and electronic materials.

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Abstract

La présente invention a pour but de proposer un stratifié plaqué cuivre qui a une bonne adhérence entre une feuille de cuivre et une résine de polyimide qui sert de résine de base, tout en ayant un effet de prévention de rouille pour la feuille de cuivre. La présente invention concerne un stratifié plaqué cuivre qui comprend : une couche de résine de primaire (B) qui est formée d'un polyimide soluble dans les solvants et disposée sur la surface d'une couche de revêtement qui est disposée sur une feuille de cuivre (A) qui n'a pas été soumise à un traitement de rugosification ; et une couche de polyimide (D) qui est directement liée sur la couche de résine de primaire (B). Le stratifié plaqué cuivre satisfait les conditions (1)-(4) décrites ci-après. La présente invention concerne également un tableau de connexions qui utilise le stratifié plaqué cuivre. (1) La couche de revêtement est configurée d'une couche Ni et d'une couche Cr qui sont stratifiées de façon séquentielle à partir de la surface de la feuille de cuivre. (2) La quantité de revêtement de Ni et la quantité de revêtement de Cr dans la couche de revêtement sont respectivement 15-440 μg/dm2 et 15-210 μg/dm2. (3) L'épaisseur maximale de la couche de revêtement est 0,5-5 nm et l'épaisseur minimale de la couche de revêtement est 80 % ou plus de l'épaisseur maximale. (4) Le polyimide soluble dans les solvants est une résine de polyimide à cycle fermé, spécifique.
PCT/JP2012/002063 2012-03-26 2012-03-26 Stratifié plaqué cuivre ayant une couche de primaire et tableau de connexions l'utilisant Ceased WO2013144992A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018047933A1 (fr) * 2016-09-12 2018-03-15 古河電気工業株式会社 Feuille de cuivre et stratifié cuivré comprenant celle-ci
JP2020128537A (ja) * 2016-08-25 2020-08-27 エルジー・ケム・リミテッド ジアミン化合物及びその製造方法
KR20200139577A (ko) * 2019-06-04 2020-12-14 삼성전자주식회사 폴리(아미드-이미드) 코폴리머, 폴리(아미드-이미드) 코폴리머 제조용 조성물, 폴리(아미드-이미드) 코폴리머를 포함하는 성형품 및 표시 장치

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JP2020128537A (ja) * 2016-08-25 2020-08-27 エルジー・ケム・リミテッド ジアミン化合物及びその製造方法
US11319282B2 (en) 2016-08-25 2022-05-03 Lg Chem, Ltd. Diamine compound and method for producing same
WO2018047933A1 (fr) * 2016-09-12 2018-03-15 古河電気工業株式会社 Feuille de cuivre et stratifié cuivré comprenant celle-ci
JPWO2018047933A1 (ja) * 2016-09-12 2018-09-06 古河電気工業株式会社 銅箔およびこれを有する銅張積層板
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CN109642338B (zh) * 2016-09-12 2021-02-09 古河电气工业株式会社 铜箔以及具有该铜箔的覆铜板
KR20200139577A (ko) * 2019-06-04 2020-12-14 삼성전자주식회사 폴리(아미드-이미드) 코폴리머, 폴리(아미드-이미드) 코폴리머 제조용 조성물, 폴리(아미드-이미드) 코폴리머를 포함하는 성형품 및 표시 장치
US11535711B2 (en) * 2019-06-04 2022-12-27 Samsung Electronics Co., Ltd. Poly(amide-imide) copolymer, composition for preparing same, article including same, and display device including the article
KR102782854B1 (ko) 2019-06-04 2025-03-14 삼성전자주식회사 폴리(아미드-이미드) 코폴리머, 폴리(아미드-이미드) 코폴리머 제조용 조성물, 폴리(아미드-이미드) 코폴리머를 포함하는 성형품 및 표시 장치

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