US20040043232A1 - Laminate and use thereof - Google Patents

Laminate and use thereof Download PDF

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Publication number
US20040043232A1
US20040043232A1 US10/069,047 US6904702A US2004043232A1 US 20040043232 A1 US20040043232 A1 US 20040043232A1 US 6904702 A US6904702 A US 6904702A US 2004043232 A1 US2004043232 A1 US 2004043232A1
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United States
Prior art keywords
layer
insulating layer
etching
organic group
divalent organic
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Abandoned
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US10/069,047
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English (en)
Inventor
Katsuya Sakayori
Shigeki Kawano
Hiroko Amasaki
Hidetsugu Tazawa
Kazunari Ikeda
Kouhei Ohno
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Assigned to DAI NIPPON PRINTING CO., LTD. reassignment DAI NIPPON PRINTING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AMASAKI, HIROKO, IKEDA, KAZUNARI, KAWANO, SHIGEKI, OHNO, KOUHEI, SAKAYORI, KATSUYA, TAZAWA, HIDETSUGU
Publication of US20040043232A1 publication Critical patent/US20040043232A1/en
Priority to US12/911,263 priority Critical patent/US8252423B2/en
Abandoned legal-status Critical Current

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/127—Structure or manufacture of heads, e.g. inductive
    • G11B5/147—Structure or manufacture of heads, e.g. inductive with cores being composed of metal sheets, i.e. laminated cores with cores composed of isolated magnetic layers, e.g. sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/002—Etching of the substrate by chemical or physical means by liquid chemical etching
    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B2220/00—Record carriers by type
    • G11B2220/20—Disc-shaped record carriers
    • G11B2220/23—Disc-shaped record carriers characterised in that the disc has a specific layer structure
    • G11B2220/235—Multilayer discs, i.e. multiple recording layers accessed from the same side
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B2220/00—Record carriers by type
    • G11B2220/20—Disc-shaped record carriers
    • G11B2220/25—Disc-shaped record carriers characterised in that the disc is based on a specific recording technology
    • G11B2220/2508—Magnetic discs
    • G11B2220/2516—Hard disks
    • 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
    • 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
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
    • 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
    • H05K2201/0183—Dielectric layers
    • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide

Definitions

  • the present invention relates to a laminate suitable for etching, by wet process, of a plurality of resin layers constituting an insulating layer in a laminate having a layer construction of first inorganic material layer (mainly metal layer)/insulating layer/second inorganic material layer (mainly metal layer) or a layer construction of inorganic material layer (mainly metal layer)/insulating layer, an insulating film, and an electronic circuit component, particularly a suspension for hard disk drives, produced by etching of the laminate by the wet process.
  • Pattern formation methods used in the formation of such wiring and circuits include: a method which comprises the steps of etching a metal layer, provided on a substrate having a layer construction of metal layer/insulating layer/metal layer, with an acidic solution, such as a ferric chloride solution, to form wirings, and, in order to provide layer-to-layer continuity, then subjecting the insulating layer in a dry state to dry etching, such as plasma etching or laser etching, or wet etching, for example, with hydrazine to remove the insulating layer to form a desired shape (Japanese Patent-Laid Open No.
  • the warpage ⁇ of this substrate can be calculated according to the following equation (Miyaaki and Miki, NITTO TECHNICAL REPORT, 35 (3), 1 (1997)).
  • ⁇ 31 ⁇ ⁇ E 1 ⁇ E 2 2 ⁇ h ⁇ ( E 1 2 + 14 ⁇ ⁇ E 1 ⁇ E 2 2 + E 2 2 ) ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ T
  • E1 modulus of the metal
  • E2 modulus of the insulating layer
  • ⁇ T temperature difference
  • h layer thickness 1 : wiring length.
  • the coefficient of thermal expansion of the metal layer should be made identical to the coefficient of thermal expansion of the insulating layer.
  • the use of a low expansion polyimide as the insulating layer in the laminate has been proposed (U.S. Pat. No. 4,543,295 and Japanese Patent Laid-Open Nos. 18426/1980 and 25267/1977).
  • the low-expansion polyimide is not generally thermoplastic, the adhesion to the metal layers is poor making it difficult to provide adhesive strength high enough to withstand practical use. It is known that, in order to overcome this problem, a thermoplastic polyimide resin or epoxy resin having good adhesion to the metal layers is used as an adhesive layer between the metal layer and the insulating layer (core layer) of the low-expansion polyimide (Japanese Patent Laid-Open No. 58428/1995).
  • the thickness of the low expansion core insulating layer is made larger than the thickness of the adhesive layer to avoid the appearance of warpage in the whole laminate.
  • the thinner the adhesive layer the better the effect of preventing warpage.
  • Excessively small thickness of the adhesive layer is detrimental to the adhesion.
  • the total thickness of the upper and lower adhesive layers provided respectively on the upper side and the lower side of the core insulating layer is not more than the half of the thickness of the core insulating layer, the warpage is less likely to occur. For this reason, for commercially available laminates, the total thickness of the adhesive layers is in many cases not more than the half of the thickness of the core insulating layer (Japanese Patent Laid-Open No. 245587/1989).
  • the wireless suspension is mainly formed of a laminate of first metal layer/adhesive insulating layer/core insulating layer/adhesive insulating layer/second metal layer.
  • An example of the laminate comprises a first metal layer of a copper alloy foil, a second metal layer of a stainless steel foil, and an insulating layer composed of a core insulating layer and an adhesive insulating layer stacked on both sides of the core insulating layer.
  • the wireless suspension For components called the wireless suspension, there are two production methods, that is, an additive method wherein wirings are mainly formed through plating, and a subtractive method wherein a copper foil is etched to form wirings.
  • an additive method wherein wirings are mainly formed through plating
  • a subtractive method wherein a copper foil is etched to form wirings.
  • plasma etching is used for patterning a polyimide as the insulating layer.
  • the laminate as the material before etching for wireless suspensions has hitherto been etched only by the dry process.
  • etching is carried out for sheet by sheet (sheet method). Therefore, disadvantageously, the productivity is low, and, in addition, sine the apparatus is expensive, the production cost is very high.
  • sheet method sheet method
  • the productivity is low, and, in addition, sine the apparatus is expensive, the production cost is very high.
  • the wet process a continuous product can be continuously etched. Therefore, advantageously, the productivity is high, and, in addition, the apparatus cost is low.
  • laminates for wireless suspensions required to satisfy severe specifications however, the wet process could not have been put to practical use for the following reason.
  • the adhesive used as a part of the insulating layer in the laminate for wireless suspension is mainly formed of a polyimide resin from the viewpoint of the necessity of ensuring a high level of insulation reliability.
  • imparting thermoplasticity is a general method for imparting adhesion to the polyimide resin. The introduction of a flexible structure, which can impart thermoplasticity, into the skeleton of the polyimide resin, however, leads to a tendency such that the chemical resistance is increased.
  • etching rate refers to the degree of a reduction in film thickness per unit time caused by etching.
  • FIG. 1 is a conceptual cross-sectional view showing the etching shape of a laminate wherein a laminate for a wireless suspension, having a layer construction of first metal layer/adhesive insulating layer/core insulating layer/adhesive insulating layer/second metal layer, which has hitherto been etched only by the dry process, has been etched by the wet process from the first metal layer side.
  • numeral 1 designates a core insulating layer formed of a low expansion polyimide resin.
  • a first metal layer 2 is provided on one side of the core insulating layer 1 through an adhesive insulting layer 4 .
  • a second metal layer 3 is provided on the other side of the core insulating layer 1 through the adhesive insulating layer 4 .
  • the etching rate of the adhesive insulating layer 4 is lower than that of the core insulating layer 1 , the adhesive insulating layer 4 in its portion remaining unetched is left in the form of the eaves of a roof. Therefore, in the whole insulating layer, the etching shape is uneven.
  • any polyimide resin, used for an adhesive insulating layer in a laminate for a wireless suspension having the above layer construction, which is suitable for etching by the wet process and has excellent adhesion, is not known.
  • it is an object of the present invention is to provide a laminate having a layer construction of first inorganic material layer (mainly metal layer)/insulating layer/second inorganic material layer (mainly metal layer) or a layer construction of inorganic material layer (mainly metal layer)/insulating layer, the insulating layer having a multi-layer structure of two or more resin layers of a core insulating layer and an adhesive insulating layer, wherein the laminate has the adhesive insulating layer, which can realize optimal etching, and has a polyimide resin which is suitable for etching by the wet process and has excellent adhesion, to provide an insulating film for the formation of the laminate, and to provide an electronic circuit component using the same.
  • the present inventors have made extensive and intensive studies on various polyimide resins which, when a multi-layer structure of two or more resin layers is adopted in an insulating layer in a laminate having a layer construction of first inorganic material layer (mainly metal layer)/insulating layer/second inorganic material layer (mainly metal layer) or a layer construction of inorganic material layer (mainly metal layer)/insulating layer, can provide a good etching shape as a resin for the insulating layer.
  • thermoplastic polyimide resin having good adhesion
  • the presence of a specific structure within the resin skeleton can accelerate the etching rate.
  • the etching rate can be made close to the etching rate of the low expansion polyimide which structurally has a high etching rate, and a good etching shape can be provided even in etching by the wet process.
  • the laminate according to the present invention has a layer construction of first inorganic material layer/insulating layer/second inorganic material layer or a layer construction of inorganic material layer/insulating layer, said insulating layer having a multi-layer structure of two or more resin layers, at least one of the layers constituting the insulating layer being formed of a polyimide resin which comprises repeating units represented by formula (1) and has a glass transition point of 150 to 360° C. and is dissolvable in a basic solution at a rate of more than 3 ⁇ m/min, preferably more than 5 ⁇ m/min, most preferably more than 8 ⁇ m/min:
  • R 1 and R 2 each represent a divalent organic group and may have a single structure or a combination of two or more structures; and n is an integer of two or more.
  • Another laminate according to the present invention has a layer construction of first inorganic material layer/insulating layer/second inorganic material layer or a layer construction of inorganic material layer/insulating layer, said insulating layer having a multi-layer structure of two or more resin layers, at least one layer constituting the insulating layer being formed of a polyimide resin which comprises repeating units represented by formula (2) and has a glass transition point of 150 to 360° C. and is dissolvable in a basic solution at a rate of more than 3 ⁇ m/min, preferably more than 5 ⁇ m/min, most preferably more than 8 ⁇ m/min:
  • R 1 and R 2 each represent a divalent organic group and may have a single structure or a combination of two or more structures;
  • R 3 represents at least one acid dianhydride selected from the group consisting of diphenylsulfone-2,3,3′,4′-tetracarboxylic acid dianhydride, diphenylsulfone-2,2′,3,3′-tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride, 2,3,3′,4′-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3′,4,4′-diphenyl ether tetracarboxylic acid dianhydride, and 1,4,5
  • conditions for determining the dissolution rate are preferably such that the dissolution rate is the highest in the etching liquid used.
  • 70° C. in a dip method is described as conditions for determining the dissolution rate.
  • the present invention is, however, not limited to this.
  • it is considered that the etching rate and the etching shape in spray etching are better than those in the dip method.
  • the etching shape greatly depends upon etching method and conditions. A good etching shape of the laminate can be realized when the etching rate is not less than 3 ⁇ m/min at the highest etching rate in a method and conditions in which etching can be actually carried out.
  • the polyimide resin may be generally any one so far as the resin has a polyimide structure.
  • the polyimide resin may be in the form of a film before stacking.
  • the polyimide may be coated in the form of a solution or a solution of a precursor followed by drying or imidation to form a resin layer.
  • n is an integer of 1 to 15.
  • 100% of the divalent organic group contained in R 1 in formula (1) or (2) is accounted for by a divalent organic group represented by formula (3) and not less than 30%, preferably not less than 80%, in terms of molar fraction of the divalent organic group contained in R 2 is accounted for by a divalent organic group represented by formula (4):
  • At least one of the resin layers (insulating layers) constituting the insulating layer in the laminate according to the present invention is formed of a low expansion resin having a coefficient of expansion of 0 to 40 ppm.
  • a low expansion polyimide resin is preferred from the viewpoint of suitability for etching.
  • the use of the low expansion resin enables the coefficient of thermal expansion of the low expansion resin in the insulating layer to be made close to the coefficient of thermal expansion of the inorganic material layer. This can prevent warpage of the laminate.
  • At least one layer should be formed of a polyimide resin.
  • all the resin layers constituting the insulating layer may be formed of a polyimide resin.
  • the insulating layer which forms an interface with at least one of the inorganic material layers, is preferably formed of a polyimide resin such that 100% of the divalent organic group contained in R 1 in formula (1) or (2) is accounted for by a divalent organic group represented by formula (3) and not less than 80% in terms of molar fraction of the divalent organic group contained in R 2 is accounted for by a divalent organic group represented by formula (4).
  • the insulating layer included in the layer construction of the laminate has a laminate structure of first insulating layer/second insulating layer/third insulating layer, the first insulating layer and the third insulating layer are formed of a polyimide resin having a structure such that 100% of the divalent organic group contained in R 1 in formula (1) or (2) is accounted for by a divalent organic group represented by formula (3) and not less than 80% in terms of molar fraction of the divalent organic group contained in R 2 is accounted for by a divalent organic group represented by formula (4), and the second insulating layer is formed of a low expansion polyimide resin having a coefficient of expansion of 0 to 40 ppm.
  • the inorganic material layers in the laminate according to the present invention may be such that both the inorganic material layers are formed of copper alloy, both the inorganic material layers are formed of copper, one of the inorganic material layers is formed of copper with the other inorganic material layer being formed of copper alloy, or one of the inorganic material layers is formed of copper or copper alloy with the other inorganic material layer being formed of stainless steel.
  • the insulating film according to the present invention comprises two or more resin layers, at least one of the resin layers being formed of a polyimide resin which has a structure comprising repeating units represented by formula (1) and has a glass transition point of 150 to 360° C. and is dissolvable in a basic solution at a rate of more than 3 pm/min.
  • Another insulating film according to the present invention comprises two or more resin layers, at least one of the resin layers being formed of a polyimide resin which has a structure comprising repeating units represented by formula (2) and has a glass transition point of 150 to 360° C. and is dissolvable in a basic solution at a rate of more than 3 ⁇ m/min.
  • the insulating film according to the present invention is useful as an intermediate material for stacking onto an inorganic material layer.
  • the construction of the insulating film according to the present invention may be the same as the construction of the insulating layer in the laminate according to the present invention.
  • At least one of the resin layers (insulating layers) constituting the insulating film according to the present invention is formed of a low expansion polyimide resin having a coefficient of expansion of 0 to 40 ppm.
  • the use of the low expansion polyimide resin enables the coefficient of thermal expansion of the polyimide resin to be made close to the coefficient of thermal expansion of the inorganic material layer. Therefore, when this insulating film is stacked onto an inorganic material layer, the warpage of the laminate can be prevented.
  • the laminate or insulating film according to the present invention may be etched to produce electronic circuit components.
  • Electronic circuit components which can be suitably produced from the laminate or insulating film according to the present invention, include suspensions for hard disk drives (HDDs).
  • HDDs hard disk drives
  • Etching by the dry process or etching by the wet process is applicable to etching of the laminate or insulating film according to the present invention.
  • the laminate or insulating film according to the present invention at least one of the layers constituting the insulating layer is formed of a polyimide resin which comprises repeating units represented by formula (1) or (2) and has a glass transition point of 150 to 360° C. and is dissolvable in a basic solution at a rate of more than 3 ⁇ m/min.
  • a basic solution may be used in etching by the wet process of the insulating layer in the laminate or insulating film according to the present invention.
  • the basic solution is preferably an alkali-amine solution, for example, an alkali-amine solution described in Japanese Patent Laid-Open No. 195214/1998.
  • the base component may be either an organic base or an inorganic base, or alternatively, may be a mixture of the above bases.
  • the basic solution preferably has pH 8 to 14, particularly preferably pH 12 to 14.
  • the 90-degree peel strength from the resin or inorganic material, which forms an interface therewith is preferably not less than 100 g/cm, more preferably not less than 300 g/cm, still more preferably not less than 700 g/cm.
  • the insulating film according to the present invention may be stacked onto an inorganic material layer to form a laminate which is then etched, or alternatively, may be etched before stacking.
  • the insulating film may be used as follows.
  • An inorganic material layer which serves as a substrate with wiring being formed thereon, is bonded onto both sides of the insulating film, and the insulating film is then etched.
  • the insulating film is bonded to the substrate. Thereafter, an inorganic material layer is applied onto the surface of the insulating film, and the inorganic layer and the insulating film are etched.
  • a previously etched insulating film is applied to an inorganic material layer.
  • a film formed by coating of a resin or a resin film may be used in the insulating layer in the laminate or the insulating film according to the present invention.
  • An object of the second invention is to provide a laminate having a laminate construction of first metal layer/insulating layer/second metal layer or a laminate construction of metal layer/insulating layer, the insulating layer comprising a plurality of layers, which laminate enables the insulating layer having an adhesive layer to be etched under optimal conditions, particularly a laminate best suited for etching by wet process which can realize continuous etching of a continuous laminate, has high productivity, and, in addition, has low apparatus cost.
  • the present inventors have made extensive and intensive studies on the etching rate ratio of resin layers, which can provide a good etching shape, in a laminate having a layer construction of first inorganic material layer (mainly metal layer)/insulating layer/second inorganic material layer (mainly metal layer) or a layer construction of inorganic material layer (mainly metal layer)/insulating layer wherein the insulating layer in the laminate has a multi-layer structure of two or more resin layers.
  • a good etching shape is obtained when the etching rate ratio of the resin layers falls within the range of 6:1 to 1:1, preferably 4:1 to 1:1.
  • a laminate having a layer construction of first inorganic material layer/insulating layer/second inorganic material layer or a layer construction of inorganic material layer/insulating layer, the insulating layer having a multi-layer structure of two or more resin layers, the ratio of the etching rate of the resin layer having a higher etching rate to the etching rate of the resin layer having a lower etching rate in the insulating layer being in the range of 6:1 to 1:1, preferably in the range of 4:1 to 1:1.
  • the etching rate refers to the degree of a reduction in film thickness per unit time caused by etching.
  • the adhesive strength of the adhesive layer to the inorganic material layer or the core insulating layer is preferably not less than 300 g/cm for all the adherends, more preferably not less than 1000 g/cm for all the adherends.
  • Inorganic materials usable in the laminate according to the present invention include, but are not particularly limited to, metals, single crystal silicon, and metal oxides.
  • Metals include, but are not particularly limited to pure metals, such as copper and iron, and alloys such as stainless steel. Further, metals having thereon a nonmetallic inorganic material layer, for example, a ceramic layer, produced by surface treating metals may also be used.
  • a laminate of a highly elastic metal, such as stainless steel, and a copper foil or a copper alloy foil as wiring is preferred.
  • an insulating film comprising two or more resin layers, the ratio of the etching rate of the resin layer having a higher etching rate to the etching rate of the resin layer having a lower etching rate being in the range of 6:1 to 1:1.
  • the laminate according to the present invention may be produced by any process without particular limitation.
  • Specific examples of production processes include: a process which comprises the steps of either coating a polyimide solution directly on a metal and drying the coated metal, or coating a precursor of polyimide onto a metal, drying the coated metal and thermally imidating the precursor, thereby forming an adhesive insulating layer onto the metal, and then thermally contact bonding the adhesive insulating layer to a film as a core insulating layer; and a process which comprises the steps of coating a solution of polyimide resin, which can serve as the core insulating layer, or a precursor thereof onto an polyimide adhesive insulating layer provided on a metal, drying the coated metal, or thermally imidating the precursor after the drying, to provide a core insulating layer, providing an adhesive insulating layer on the core insulating layer according to the above procedure, and thermally contact bonding the assembly to a metal to prepare a laminate material.
  • a process may be adopted wherein the insulating film according to
  • the laminate or insulating film according to the present invention can be etched, preferably by wet process, to produce electronic circuit components.
  • a method may be adopted wherein the insulating film according to the present invention is stacked onto an inorganic material to prepare a laminate which is then etched, preferably by the wet process, to prepare an electronic circuit component.
  • the “laminate” or “stacking” means not only stacking of a film form but also the formation of a specific layer onto a substrate.
  • FIG. 1 is a conceptual diagram showing the etching shape of a laminate in its cross section, wherein a laminate for a wireless suspension, having a layer construction of first metal layer/adhesive insulating layer/core insulating layer/adhesive insulating layer/second metal layer, which has hitherto been etched only by the dry process, has been etched by the wet process from the first metal layer side;
  • FIG. 2 is an SEM (scanning electron microscope) photograph of an etching shape of a laminate using polyimide A prepared in Example A2;
  • FIG. 3 is a cross-sectional view of a laminate before processing and the laminate after plasma etching or wet etching with an alkali solution;
  • FIG. 4 is a graph wherein dipping time (sec) is plotted as abscissa and degree of reduction in film thickness ( ⁇ M), defined as a value obtained by subtracting film thickness after dipping from initial film thickness, is plotted as ordinate;
  • FIG. 5 is an SEM (scanning electron microscope) photograph showing an etching shape of a three-layer material using film A with an adhesive layer;
  • FIG. 6 is an SEM (scanning electron microscope) photograph showing an etching shape of a three-layer material using film B with an adhesive layer;
  • FIG. 7 is a schematic illustration of the photograph shown in FIG. 6;
  • FIG. 8 is an SEM (scanning electron microscope) photograph showing an etching shape of a three-layer material using film C with an adhesive layer;
  • FIG. 9 is an XPS chart of a dry etching sample
  • FIG. 10 is an XPS chart showing detailed measured data of portions corresponding to nitrogen and fluorine;
  • FIG. 11 is an XPS chart showing detailed measured data of portions corresponding to nitrogen and fluorine;
  • FIG. 12 is an XPS chart showing the results of measurement of a wet etching sample
  • FIG. 13 is an XPS chart showing the results of measurement of a wet etching sample
  • FIG. 14 is an XPS chart showing the results of measurement of a wet etching sample
  • FIG. 15 is an XPS chart of a reference of a plasma etching sample.
  • FIG. 16 is an XPS chart of a reference of a wet etching sample.
  • the insulating layer portion has a laminate structure such that a thermoplastic adhesive insulating layer is provided on one side or both sides of a low expansion core insulating layer.
  • an adhesive resin has a high coefficient of thermal expansion and, thus, when as such is stacked onto a metal, causes a warpage.
  • the thickness of the low expansion core insulating layer is made larger than the thickness of the adhesive insulating layer to prevent noticeable warpage from appearing in the whole laminate.
  • the smaller the thickness of the adhesive insulating layer the better the effect of preventing warpage.
  • the thickness is excessively small, however, the adhesion is sometimes deteriorated.
  • the warpage is less likely to appear.
  • etching the laminate by the wet process when the plurality of insulating resin layers are different from each other in etching rate, in general, the edge shape is not straight and the layer having a lower etching rate remains unetched.
  • the etching rate of the adhesive insulating layer when the etching rate of the adhesive insulating layer is low, the etching shape is such that the upper and lower surfaces are projected.
  • the etching rate relationship is opposite to the above relationship, the adhesive insulating layer is etched earlier. In this case, the resultant etching shape is such that the center portion is projected.
  • Etching of a polyimide resin with an alkali solution will be taken as an example.
  • the imide bond is attacked by hydroxide ions in the solution, resulting in the formation of polyamic acid.
  • the solubility of the polyamic acid in the alkali solution is higher than the solubility of the polyimide in the alkali solution. Since the amide group of the amic acid is further attacked by hydroxide ions and consequently is hydrolyzed to lower the molecular weight of the polymer, the solubility is improved. When a hydrolyzable group is present in the molecular chain, this site is sometimes hydrolyzed.
  • General-purpose low expansion polyimides are divided in terms of constitution into polyimides using pyromellitic acid dianhydride as the main skeleton and polyimides using biphthalic acid dianhydride as the main skeleton. It is known that, when pyromellitic acid dianhydride is used in the insulating layer, alkali resistance is less likely to develop, for example, due to an influence of an electronic factor derived from structure, that is, etchability with an alkali is poor. For this reason, preferably, the low expansion polyimide serving as the core insulating layer in the insulating layer of the laminate according to the present invention has pyromellitic acid dianhydride in its structure.
  • biphthalic acid dianhydride polyimides are known to have good alkali resistance.
  • the selection of diamine as another material for the polyimide is preferred from the viewpoint of suppressing the development of the alkali resistance.
  • the use of the pyromellitic acid dianhydride as the main skeleton is difficult. This is because, when pyromellitic acid dianhydride is used, the thermoplasticity is less likely to develop and, thus, the adhesion is not very good. Therefore, the present inventors have paid attention to bistrimellitic acid dianhydride as an acid dianhydride which has a structure similar to pyromellitic acid dianhydride, has in its skeleton an ester bond hydrolyzable with hydroxide ions, and has a skeleton having a flexibility high enough to develop thermoplasticity.
  • trimellitic acid per se has a structure similar to pyromellitic acid, there is no particular limitation on a site for connecting trimellitic acid.
  • bistrimellitic acid dianhydride having a hydrocarbon diol is preferred from the viewpoint of easily imparting thermoplasticity to the whole resin.
  • polyimide resins which have been produced using ethylene glycol bistrimellitic acid dianhydride (abbreviation: TMEG) as a starting material, have hitherto been fully studied and have been reported to have good adhesion (Japanese Patent Laid-Open Nos. 152647/1998 and 168187/1998).
  • TMEG ethylene glycol bistrimellitic acid dianhydride
  • the resin for forming the adhesive insulating layer used in the laminate or insulating film according to the present invention is mainly a polyimide or a resin similar thereto.
  • the resin is not particularly limited, so far as a skeleton derived from bistrimellitic acid dianhydride is present within the skeleton of the resin, and the imide bond content has no influence so far as the resin has heat resistance and insulating properties.
  • a material which has a structure similar to the above-described ethylene glycol bistrimellitic acid dianhydride (abbreviation: TMEG) and wherein the number of carbon atoms between oxygen atoms at the ethylene glycol site is not 2 , is also considered to have the same hydrolysis resistance.
  • TMEG is most preferred from the viewpoints of cost and reactivity with an alkali.
  • other acid anhydride component may be contained in the structure in such an amount that is not detrimental to the properties.
  • Other acid anhydrides include, but are not particularly limited to, in addition to bistrimellitic acid dianhydride, diphenylsulfone-2,3,3′,4′-tetracarboxylic acid dianhydride, diphenylsulfone-2,2′,3,3′-tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride, 2,3,3′,4′-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3′,4,4′
  • Diamines as the starting material of the polyimide resin used in the adhesive insulating layer include aliphatic diamines, aromatic diamines represented by formula (5), or aromatic diamines represented by formula (6). These diamines may be used solely or as a mixture of two or more.
  • R 3 represents an alkyl, fluorine-substituted alkyl, alkoxyl, or halogen group; and n is an integer of 0 to 4, provided that nR 3 s may be the same or different; and
  • A represents a bond group selected from the group consisting of a group of single bonds, —O—, —CH 2 —, —CO—, —C(CH 3 ) 2 —, C(CF 3 ) 2 —, —S—; and —SO 2 —;
  • R 4 , and R 5 may be the same or different and have the same meanings as R 3 ;
  • x, y, z, and m are an integer of 0 to 4; and (m+1) As may be the same or different.
  • Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
  • aromatic diamines represented by formula (5) or (6) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 1,3-bis(3-aminophenoxy)benzene, 1,4
  • the diamine as the starting material for the polyimide resin used in the adhesive insulating layer is preferably an aromatic diamine rather than the aliphatic diamine, for example, from the viewpoint of heat resistance.
  • the thermoplastic resin used in the insulating layer of the laminate according to the present invention is a resin having a glass transition point (Tg) below the thermal decomposition temperature.
  • Tg glass transition point
  • the glass transition point is determined by differential thermal analysis. If necessary, however, the tan ⁇ peak as determined by dynamic viscoelasticity measurement may be regarded as the glass transition point.
  • Tg was determined based on the dynamic viscoelasticity. For example, when the resin is brittle and cannot withstand the measurement of the dynamic viscoelasticity, however, the glass transition point may be determined by the differential thermal analysis.
  • the glass transition point is preferably 360° C. or below.
  • the glass transition point is preferably 150° C. or above from the viewpoint of heat resistance such as soldering heat resistance.
  • a resin, wherein the storage modulus is as low as possible at a temperature of the glass transition point or above, is likely to develop adhesion even when any high pressure is not applied.
  • the etching rate refers to the degree of a reduction in film thickness per unit time when the laminate is brought into contact with an etching liquid.
  • the temperature may be any value so far as the etching liquid is kept in the liquid state.
  • the laminate may be brought into contact with the etching liquid by any method, and examples thereof include dipping and spraying.
  • An additive may be added to the resin used in the laminate according to the present invention so far as the etchability is not sacrificed.
  • the etching temperature is preferably 40° C. or above, more preferably 60° C. or above. Since, however, a component, which is evaporated at that temperature, is contained in the etching liquid, when the vaporization of this component results in deteriorated service life of the etching liquid and operability, the etching is preferably carried out at a temperature such that such properties are not deteriorated.
  • the etching liquid is in many cases soluble in water. In this case, the etching liquid is likely to boil. Therefore, the etching is preferably carried out at a temperature of 110° C. or below.
  • the etching rate is measured at 70° C.
  • the temperature 70° C. was merely selected as a measure. Therefore, the etching is preferably carried out under temperature and other conditions which permit the etching liquid to realize the optimal etching.
  • a resin having an etching rate of lower than 3 ⁇ m/min causes problems such as blind over edging or a sectional form which is not straight. Therefore, this type of resin is unfavorable, and the laminate using this type of resin cannot be put to practical use.
  • a basic solution may be used in etching by the wet process of the insulating layer in the laminate or insulating film according to the present invention.
  • the basic solution is preferably an alkali-amine solution, for example, an alkali-amine solution described in Japanese Patent Laid-Open No. 195214/1998.
  • the base component may be either an organic base or an inorganic base, or alternatively, may be a mixture of the above bases.
  • the basic solution preferably has pH 8 to 14, particularly preferably pH 12 to 14.
  • the 90-degree peel strength from the resin or inorganic material, which forms an interface therewith is preferably not less than 100 g/cm, more preferably not less than 300 g/cm, still more preferably not less than 700 g/cm.
  • the polyimide resin used in the adhesive insulating layer may be synthesized by any method without particular limitation, and examples thereof include: a method wherein polyamic acid is produced in a solution and coated followed by thermal imidation; and a method wherein heating under reflux in a solution is carried out for imidation.
  • a dehydration catalyst such as acetic anhydride, may be adopted for the synthesis of the polyimide resin.
  • Inorganic materials usable in the laminate according to the present invention include, but are not particularly limited to, metals, single crystal silicon, and metal oxides.
  • Metals include, but are not particularly limited to pure metals, such as copper and iron, and alloys such as stainless steel.
  • Metals having thereon a nonmetallic inorganic material layer, for example, a ceramic layer, produced by surface treating metals may also be used.
  • a laminate of a highly elastic metal, such as stainless steel, and a copper foil or a copper alloy foil as wiring is preferred.
  • the laminate may be produced by any process without particular limitation.
  • Specific examples of production processes include: a process which comprises the steps of either coating a polyimide solution directly on a metal and drying the coated metal, or coating a precursor of polyimide onto a metal, drying the coated metal and thermally imidating the precursor, thereby forming an adhesive insulating layer onto the metal, and then thermally contact bonding the adhesive insulating layer to a film as a core insulating layer; and a process which comprises the steps of coating a solution of polyimide resin, which can serve as the core insulating layer, or a precursor thereof onto a polyimide adhesive insulating layer provided on a metal, drying the coated metal, or thermally imidating the precursor after the drying, to provide a core insulating layer, providing an adhesive insulating layer on the core insulating layer according to the above procedure, and thermally contact bonding the assembly to a metal to prepare a laminate material.
  • a process may be adopted wherein the insulating film according to the present invention
  • the weight average molecular weight of the resin used in the adhesive insulating layer in the laminate according to the present invention is preferably 6000 to 500000, particularly preferably 8000 to 100000, from the viewpoint of suitability for production process of the laminate or film, although the suitable weight average molecular weight varies depending upon the molecular structure.
  • the molecular weight is not less than 500000, it is difficult to provide homogeneous coating.
  • the molecular weight is not more than 6000, the film formability is poor and, thus, the formation of a coating having even adhesion is difficult.
  • the adhesive may be coated in a solution form, or alternatively, other method may be used. Further, a precursor or a derivative thereof may be coated, followed by treatment to form a desired structure.
  • Electronic circuit components can be generally produced by the following method. However, the production method is not limited to the following method.
  • a photosensitive resin layer is coated or laminated on the surface of a metal, on its side where the formation of a circuit is desired, in the laminate according to the present invention.
  • a mask with a desired pattern image being drawn thereon is brought into intimate contact with the photosensitive resin layer, followed by exposure to an electromagnetic wave with wavelength to which the photosensitive resin is sensitive. Thereafter, when the photosensitive resin is of a positive-working type, the exposed area is eluted with a predetermined developing solution. On the other hand, when the photosensitive resin is of a negative-working type, the unexposed area is eluted with a predetermined developing solution. Thus, a desired circuit image is formed on the metal.
  • the metal with the circuit image formed thereon is then immersed in a solution capable of dissolving the metal, such as an aqueous ferric chloride solution.
  • a solution capable of dissolving the metal such as an aqueous ferric chloride solution.
  • this solution may be sprayed on the substrate.
  • the metal exposed on the surface is eluted, and the photosensitive resin is then peeled off by a predetermined peeling solution to form a circuit.
  • an insulating layer is patterned by the dry or wet process on the circuit formed on the substrate in the same manner as described above in connection with the patterning of the metal layer.
  • a mask with a predetermined pattern image being drawn thereon is intimately contacted, and an electromagnetic wave with wavelengths, to which the photosensitive resin is sensitive, is applied.
  • a predetermined developing solution is used to elute exposed areas in the case of positive-working photosensitive resin and to elute unexposed areas in the case of negative-working photosensitive resin to form a predetermined pattern.
  • the patterned product is immersed in a solution for dissolving the resin constituting the insulating layer, for example, an alkali-amine polyimide etching liquid, or alternatively, the solution is sprayed on the substrate.
  • a solution for dissolving the resin constituting the insulating layer for example, an alkali-amine polyimide etching liquid, or alternatively, the solution is sprayed on the substrate.
  • the exposed insulating layer resin is eluted, and the photosensitive resin is then separated with a predetermined peeling solution.
  • the plasma etching gas has a high temperature of 200° C. or above, the surface of the stainless steel is exposed after the removal of the resin, such as polyimide, as the insulating layer, and the exposed surface of the stainless steel is reacted with plasma to form the inorganic nitride and/or the inorganic fluoride.
  • the alkaline solution has lower reactivity with metals than with organic materials.
  • the processing temperature is low and is 100° C. or below, and the processing time is as short as several minutes. Therefore, the processing is less likely to change the surface of the stainless steel exposed after the removal of the polyimide.
  • the insulating layer has a laminate structure such that a thermoplastic adhesive layer is provided on both sides of a low expansion core insulating layer.
  • a thermoplastic adhesive layer is provided on both sides of a low expansion core insulating layer.
  • at least one layer constituting the insulating layer is formed of a polyimide resin. If necessary, all the layers constituting the insulating layer may be formed of a polyimide resin.
  • the adhesive thermoplastic resin used in the adhesive layer has a high coefficient of thermal expansion
  • stacking of the adhesive layer onto the metal layer is likely to cause warpage. Therefore, it is important that the thickness of the core insulating layer of a low expansion resin selected from resins having a coefficient of thermal expansion similar to that of the metal layer be made larger than the thickness of the adhesive layer to suppress the appearance of the warpage of the whole laminate on the surface of the laminate.
  • the smaller the thickness of the adhesive layer as compared with the thickness of the core insulating layer the lower the level of warpage.
  • the thickness of the adhesive layer is excessively small, the adhesion is deteriorated.
  • the total thickness of the upper and lower adhesive layers respectively overlying and underlying the core insulating layer is not more than the half of the thickness of the core insulating layer, the warpage is less likely to take place.
  • the etching shape is expected to be good.
  • the etching rate of the adhesive layer is in many cases greatly different from that of the core insulating layer.
  • the present inventors have drawn attention to the fact that, in a laminate having a layer construction of first metal layer/insulating layer/second metal layer or a layer construction of metal layer/insulating layer for high precision electronic circuit components, for example, for wireless suspensions, the maximum thickness ratio between the core insulating layer and each adhesive layer constituting the insulating layer is 4:1. Based on this, the present inventors have framed a hypothesis such that, when the adhesive layer has an etching rate of one-fourth of the etching rate of the core insulating layer, the adhesive layer and the core insulating layer are etched in an identical time and, thus, a good etching shape can be obtained. The present inventors have experimentally demonstrated that this hypothesis is correct.
  • the rate of etching of materials with an etchant is considered to vary from material to material, and is a value determined by conditions for the measurement of the etching rate. It is also considered that the etching rate would vary depending, for example, upon etching conditions, such as temperature and etching techniques. In the laminate or the insulating film according to the present invention, however, the shape after etching is important. Therefore, in the present invention, the etching rate may be measured at various temperatures, which are used in actual etching, so far as the shape after etching is good. Specifically, according to the present invention, so far as the correlation between the etching rates of the layers constituting the insulating layer satisfies specific conditions, etching under the conditions can provide a good shape after etching, independently of the temperature.
  • the etching temperature may be substantially any temperature so far as the etchant functions as desired.
  • the etching temperature is preferably between 0° C. and 110° C.
  • the etching rate generally decreases with lowering the temperature, and when the temperature is high, the etchant boils, resulting in deteriorated handleability.
  • the etching temperature is more preferably in the range of 30 to 90° C.
  • the etching is carried out at 50 to 90° C. from the viewpoint of suppressing a change in composition of the etchant, for example, due to evaporation of the component, and shortening the etching time.
  • the core insulating layer in order to prevent the warpage of the laminate, a material having a coefficient of thermal expansion identical to the metal is used.
  • the adhesive layer is formed of a thermoplastic resin from the viewpoint of imparting the adhesion.
  • the coefficient of thermal expansion of this type of the adhesive layer is larger than that of the metal layer, and, thus, this is causative of the warpage of the laminate. Therefore, preferably, the thickness of the adhesive layer is made smaller than that of the core insulating layer to prevent warpage of the laminate.
  • the total thickness of the adhesive layers is preferably not more than the half of the thickness of the core insulating layer.
  • the thickness of each layer in the adhesive layer is preferably not more than one-fourth of the thickness of the core insulating layer.
  • Etching of a polyimide resin with an alkali solution as an etching solution for resin by the wet process will be taken as an example.
  • the imide bond is attacked by hydroxide ions in the solution, resulting in the formation of polyamic acid.
  • the solubility of the polyamic acid in the alkali solution is higher than the solubility of the polyimide in the alkali solution. Since the amide group of the amic acid is further attacked by hydroxide ions and consequently is hydrolyzed to lower the molecular weight of the polymer, the solubility is considered to be improved.
  • a hydrolyzable group is present in the molecular chain, this group site is sometimes hydrolyzed.
  • the polyimide layer having a lower etching rate is disposed on a side, which is to be exposed to the etching liquid, to prevent side etching of the polyimide layer.
  • the polyimide layers may be disposed in any order from the side to be exposed to the etching liquid.
  • the polyimide layer disposed on the side to be exposed to the etching solution may be one having a higher etching rate or one having a lower etching rate.
  • an etching rate range which can provide an acceptable etching shape in the plurality of polyimide layers, is specified. Therefore, according to the theory of Japanese Patent Laid-Open No. 164084/1994, in the case of a laminate having a layer construction of polyimide layer having lower etching rate/polyimide layer having higher etching rate/polyimide layer having lower etching rate, etching should be carried out from both sides.
  • the etching rate range suitable for etching from one side has been found.
  • the resin for the adhesive layer used in the present invention is preferably mainly a polyimide or a resin similar thereto.
  • the resin is not limited thereto, and the resin is regardless of the presence of the imide bond so far as the resin has heat resistance and insulating properties.
  • the storage modulus referred to herein is a storage modulus of the adhesive at the time of bonding of the insulating layer to an adherend, for example, by contact bonding, but not a storage modulus in such a state that, in the final form of the three-layer material, the molecular structure or the like has been changed from that in the step of bonding.
  • the weight average molecular weight of the resin constituting the adhesive layer according to the present invention is preferably 6000 to 500000, particularly preferably 8000 to 100000, although the suitable weight average molecular weight depends upon the molecular structure.
  • the molecular weight is not less than 500000, it is difficult to provide homogeneous coating.
  • the molecular weight is not more than 6000, the film formability is poor and, thus, the formation of a coating having even adhesion is difficult.
  • the adhesive may be coated in a solution form, or alternatively, other method may be used. Further, a precursor or a derivative thereof may be coated, followed by treatment to form a desired structure.
  • Electronic circuit components can be generally produced by the following method.
  • a photosensitive resin layer is coated or laminated on the surface of a metal, on its side where the formation of a circuit is desired, in the laminate according to the present invention.
  • a mask with a desired pattern image drawn thereon is brought into intimate contact with the photosensitive resin layer, followed by exposure to an electromagnetic wave with wavelength to which the photosensitive resin is sensitive. Thereafter, when the photosensitive resin is of a positive-working type, the exposed area is eluted with a predetermined developing solution. On the other hand, when the photosensitive resin is of a negative-working type, the unexposed area is eluted with a predetermined developing solution.
  • a desired circuit image is formed on the metal.
  • the metal with the circuit image formed thereon is then immersed in a solution capable of dissolving the metal, such as an aqueous ferric chloride solution.
  • a solution capable of dissolving the metal such as an aqueous ferric chloride solution.
  • this solution may be sprayed on the substrate.
  • the metal exposed on the surface is eluted, and the photosensitive resin is then peeled off by a predetermined peeling solution to form a circuit.
  • the plasma etching gas has a high temperature of 200° C. or above, the surface of the stainless steel is exposed after the removal of the resin, such as polyimide, as the insulating layer, and the exposed surface of the stainless steel is reacted with plasma to form the inorganic nitride and/or the inorganic fluoride.
  • the alkaline solution has lower reactivity with metals than with organic materials.
  • the processing temperature is low and is 100° C. or below, and the processing time is as short as several minutes. Therefore, it is considered that the processing is less likely to change the surface of the stainless steel exposed after the removal of the polyimide.
  • a polyimide resin (polyimide A) composed of ethylene glycol bis-trimellitic acid dianhydride and 4,4′-diaminodiphenyl ether was used as a resin for an adhesive insulating layer
  • a polyimide resin (polyimide B) composed of 3,3′,4,4′-biphthalic acid dianhydride and 4,4′-diaminodiphenyl ether was used as a resin for an adhesive insulating layer.
  • a 12.5 ⁇ m-thick polyimide film APIKAL NPI (tradename, manufactured by Kanegafuchi Chemical Ind.
  • Each of these adhesive resins was dissolved in the form of a polyimide in N-methyl-2-pyrrolidone (abbreviation: NMP) to prepare a solution which was spin coated onto a 100 ⁇ m-thick SUS 304 plate (manufactured by Nippon Steel Corp.) having a size of 15 cm ⁇ 15 cm to a thickness of 20 to 40 ⁇ m, and the coating was dried in an oven at 180° C. for 30 min.
  • NMP N-methyl-2-pyrrolidone
  • the coated plates were cut into a size of about 1.5 cm in length ⁇ about 2 cm in width, and a cut was provided at the center of the sample plate with a cutter knife, followed by the measurement of the film thickness as an initial film thickness with a tracer type film thickness meter Dektak (Dektak 16000: tradename, manufactured by Sloan Technology). Thereafter, the sample plates were dipped in the polyimide etching liquid TPE-3000 (tradename, manufactured by Toray Engineering Co., Ltd.), which had been stirred with a magnetic stirrer regulated at 70° C.
  • TPE-3000 tradename, manufactured by Toray Engineering Co., Ltd.
  • a 12.5 ⁇ m-thick APIKAL NPI film (tradename, manufactured by Kanegafuchi Chemical Ind. Co., Ltd.) was cut into a size of 15 cm ⁇ 15 cm square which was then securely applied with a weakly pressure-sensitive adhesive tape so as not to cause cockling onto a 100 ⁇ m-thick SUS 304 plate (manufactured by Nippon Steel Corp.).
  • Polyimide A and Polyimide B as used in Example A1 were coated onto this laminate to a film thickness of 2.5 ⁇ m ⁇ 0.3 ⁇ m on a dry basis, and the coatings were dried in the same manner as in Example A1.
  • the coated film was separated from the SUS plate as the support, and the film was turned over, and the film was applied so as not to cause cockling.
  • polyimide A and polyimide B were coated to form a film.
  • the assembly was separated from the support.
  • film A with an adhesive insulating layer and film B with an adhesive insulating layer were prepared.
  • the dry film resist was dried, and was dipped in an etching liquid TPE-3000 (tradename, manufactured by Toray Engineering Co., Ltd.) which had been stirred at 70° C. with a magnetic stirrer to such an extent that a vortex took place.
  • TPE-3000 tradename, manufactured by Toray Engineering Co., Ltd.
  • the dry film resist was taken out of the etching liquid, followed by the separation of the dry film resist with a 3 wt % aqueous NaOH solution of 50° C. at a spray pressure of 1 kg.
  • the insulating layer which had been brought to the desire shape, was observed through an SEM (scanning electron microscope) photograph to examine the etching shape.
  • the etching shape of the laminate using polyimide B was such that the adhesive insulating layer was left and was projected on the core insulating layer.
  • the insulating layer could be removed by etching for about 2 min, and, although the taper angle was 45° C., the edge was linear and had a good shape.
  • An SEM (scanning electron microscope) photograph of the etching shape of the laminate using polyimide A prepared in Example A2 is shown in FIG. 2.
  • the polyimide A as used in Example A1 was coated onto a copper foil having a size of 10 cm ⁇ 10 cm and a thickness of 12 ⁇ m, and the coated copper foil was dried in an oven at 180° C. for 30 min to form an about 25 ⁇ m-thick coating. Thereafter, etching of the copper foil was carried out in 45 Baume ferric chloride having a liquid temperature of 50° C. to prepare a polyimide film (polyimide A).
  • the film of polyimide A and a 25 ⁇ m-thick APIKAL NPI film (tradename, manufactured by Kanegafuchi Chemical Ind.
  • test pieces were cut into test pieces having a length of about 1.5 cm and a width of 5 mm which were then measured with a viscoelastic measuring apparatus RSA-II (tradename, manufactured by Rheometric Scientific) under conditions of sample length 8 mm, sample width 5 mm, temperature rise rate 5° C./min, frequency 3.0 Hz, and temperature rise from room temperature to 400° C.
  • RSA-II viscoelastic measuring apparatus
  • polyimide A has a tan ⁇ peak around 170° C. and has a softening point around that temperature.
  • APIKAL NPI film (tradename, manufactured by Kanegafuchi Chemical Ind. Co., Ltd.) was found to have no tan ⁇ peak until 400° C. and to have no thermoplasticity.
  • a 2 to 3 ⁇ m-thick coating of polyimide A as used in Example A1 was formed by spin coating on the surface of the SUS substrate as the substrate both sides of which have been roughened, and the coating was dried in the same manner as in Example A1 to provide an adhesive insulating layer of Example A4 on the substrate.
  • the laminate having a layer construction of resin layer/substrate thus obtained was stacked onto each adherend, that is, a 20 ⁇ m-thick SUS 304 HTA foil (tradename, manufactured by Nippon Steel Corp.), an 18 ⁇ m-thick copper alloy foil C 7025 (tradename, manufactured by Olin Corp.), and a 75 ⁇ m-thick APIKAL NPI film (tradename, manufactured by Kanegafuchi Chemical Ind. Co., Ltd.), by vacuum contact bonding under conditions of temperature 300° C. and surface pressure 1 MPa for 10 min to prepare evaluation samples.
  • APIKAL NPI (tradename, a polyimide film with a thickness of 25 ⁇ m, manufactured by Kanegafuchi Chemical Ind. Co., Ltd.) was provided as a resin film.
  • the resin film was thermally contact bonded and stacked onto each of the adherends under conditions of 300° C. and 1 MPa to prepare evaluation samples respectively having laminate suructure of the following combinations.
  • APIKAL NPI thickness 25 ⁇ m
  • SUS 304 thickness 20 ⁇ m
  • APIKAL NPI thickness 25 ⁇ m
  • C 7025 thickness 18 ⁇ m
  • APIKAL NPI thickness 25 ⁇ m
  • APIKAL NPI thickness 75 ⁇ m
  • the APIKAL NPI film (tradename, manufactured by Kanegafuchi Chemical Ind. Co., Ltd.) was not adhered to each of the adherends by contact bonding.
  • the reason for this is believed to reside in that, as described above, the APIKAL NPI film was free from thermoplasticity.
  • polyimide A had adhesive strength as shown in Table A2, that is, provided good results. This demonstrates the following facts.
  • the thermoplasticity-free resin, when thermally contact bonded, is less likely to develop adhesive power, whereas the polyimide resin using ethylene glycol bis-trimellitic acid dianhydride according to the present invention has a very unique composition which has both properties of etchability and adhesion.
  • the laminate according to the present invention has a good shape after etching and, in the case of a continuous laminate, can be continuously etched and, even in wet etching, can be etched with high accuracy.
  • the productivity of etching is high, the apparatus cost is also advantageously low, and a good etching shape can be realized after etching.
  • Optimizing the etching rate of an adhesive insulating layer in an insulating layer of a laminate for precision electronic circuit components, such as wireless suspensions, and, in addition, rendering the adhesion of the adhesive insulating layer good means simultaneous realization of both contradictory property requirements.
  • the adoption of a polyimide resin having the above-described specific formulation as an adhesive insulating layer in the polyimide laminate and insulating film can simultaneously realize the above requirements. Therefore, the laminate having the above layer construction can be continuously wet etched, and the laminate for precision electronic circuit components can also be continuously treated. Therefore, when the wet etching is applied, etching can be carried out in an etching time which is at least one order shorter than the etching time necessary in the conventional plasma etching.
  • Insulating layers were prepared using the following thermoplastic resin varnishes and low expansion polyimide films by the following method. In this case, the following etching liquid was used for etching.
  • Thermoplastic resin varnish . . . PAA-A (tradename), polyamic acid varnish manufactured by Mitsui Chemicals Inc.; N 8020, AT 8020 (tradename), and BA 5050 (tradename), polyamide imide varnish manufactured by Toyobo Co., Ltd.; and SN-20 (tradename), PN-20 (tradename), and EN-20 (tradename), polyimide varnish manufactured by New Japan Chemical Co., Ltd.
  • Low expansion polyimide film . . . APIKAL NPI (tradename), polyimide film manufactured by Kanegafuchi Chemical Ind. Co., Ltd.; and KAPTON EN (tradename), polyimide film manufactured by Du Pont-Toray Co., Ltd.
  • Etching liquid . . . TPE-3000 (tradename), alkali-amine polyimide etching liquid manufactured by Tray Engineering Co., Ltd.
  • thermoplastic resin varnishes were spin coated onto an SUS 304 plate having a size of 15 cm ⁇ 15 cm and a thickness of 100 ⁇ m to a thickness of 20 to 40 ⁇ m.
  • the coated portions of all the varnishes [N 8020 (tradename, polyamide imide varnish manufactured by Toyobo Co., Ltd., AT 8020 (tradename, polyamide imide varnish, manufactured by Toyobo Co., Ltd.), BA 5050 (tradename, polyamide imide varnish, manufactured by Toyobo Co., Ltd.), SN-20 (tradename, polyimide varnish, manufactured by New Japan Chemical Co., Ltd.), and EN-20 (tradename, polyimide varnish, manufactured by New Japan Chemical Co., Ltd.)] except for PAA-A (tradename, polyamic acid varnish manufactured by Mitsui Chemicals Inc.) were dried in an oven at 180° C. for 30 min.
  • PAA-A (tradename, polyamic acid varnish, manufactured by Mitsui Chemicals Inc.) was dried at 120° C. for 15 min to remove the solvent, and was then subjected to predetermined treatment to conduct thermal imidation, thereby preparing a polyimide.
  • Each of the dried coated products thus obtained was cut into a size of about 1.5 cm in length ⁇ about 2 cm in width, and a cut was provided with a cutter knife at the center of the samples, followed by the measurement of the film thickness as an initial film thickness with a tracer type film thickness meter Dektak 16000 (tradename, manufactured by Sloan Technology).
  • the samples were dipped in the alkali-amine polyimide etching liquid TPE-3000 (tradename, manufactured by Toray Engineering Co., Ltd.), which had been stirred with a magnetic stirrer regulated at 70° C. to such an extent that a vortex took place, and, for each dipping time, the thickness of the film substantially in its site, where the initial film thickness had been measured, was measured with a tracer type film thickness meter Dektak 16000 (tradename, manufactured by Sloan Technology). The film thickness after dipping was subtracted from the initial film thickness to determine the degree of reduction in film thickness. The results are shown in a graph of FIG. 4 wherein the dipping time (sec) are plotted as abscissa against degree of reduction in film thickness ( ⁇ m) as ordinate.
  • TPE-3000 tradename, manufactured by Toray Engineering Co., Ltd.
  • the laminates having a layer construction of resin layer/substrate thus obtained were stacked onto each adherend, that is, a 20 ⁇ m-thick SUS 304 HTA foil (tradename, manufactured by Nippon Steel Corp.), an 18 ⁇ m-thick copper alloy foil C 7025 (tradename, manufactured by Olin Corp.), and a 75 ⁇ m-thick APIKAL NPI film (manufactured by Kanegafuchi Chemical Ind. Co., Ltd.), and vacuum contact bonding was carried out at a temperature, which provided the lowest storage modulus of each of the thermoplastic resins, at a surface pressure of 1 MPa for 10 min to prepare evaluation samples.
  • Tg the tan ⁇ peak obtained in the measurement of viscoelasticity
  • APIKAL NPI (tradename, a polyimide film with a thickness of 25 ⁇ m, manufactured by Kanegafuchi Chemical Ind. Co., Ltd.) and KAPTON EN (tradename, thickness 25 ⁇ m, manufactured by Du Pont-Toray Co., Ltd.) were provided as resin films.
  • the resin films were thermally contact bonded and stacked to each of the adherends under conditions of 300° C. and 1 MPa to prepare evaluation samples respectively having a laminate structure of the following combinations.
  • APIKAL NPI thickness 25 ⁇ m
  • SUS 304 thickness 20 ⁇ m
  • APIKAL NPI thickness 25 ⁇ m
  • C 7025 thickness 18 ⁇ m
  • APIKAL NPI thickness 25 ⁇ m
  • APIKAL NPI thickness 75 ⁇ m
  • KAPTON EN (thickness 25 ⁇ m)-SUS 304 (thickness 20 ⁇ m)
  • KAPTON EN (thickness 25 ⁇ m)-C 7025 (thickness 18 ⁇ m)
  • KAPTON EN (thickness 25 ⁇ m)-APIKAL NPI (thickness 75 ⁇ m)
  • a 12.5 ⁇ m-thick APIKAL NPI film (tradename, a polyimide film manufactured by Kanegafuchi Chemical Ind. Co., Ltd.) was cut into a size of 15 cm ⁇ 15 cm square the periphery of which was then securely applied onto a 100 ⁇ m-thick SUS 304 plate with a weakly pressure-sensitive adhesive tape so as not to cause cockling, thereby flattening the surface of the polyimide film.
  • EN-20 (tradename, polyimide varnish, manufactured by New Japan Chemical Co., Ltd.) was spin coated as an adhesive layer to a film thickness of 2.5 ⁇ m ⁇ 0.3 ⁇ m on a dry basis, and the film was then dried. Thereafter, the coated film was separated from the SUS plate as the support, and the polyimide film was turned over, and the polyimide film was again applied to the SUS plate so as not to cause cockling. In the same manner as described above, a film of EN-20 was formed. The assembly was separated from the support. Thus, film A with an adhesive layer was prepared.
  • a film of PAA-A was formed on both sides of a 12.5 ⁇ m-thick APIKAL NPI film to prepare film B with an adhesive layer
  • a film of EN-20 was provided on both sides of a 12.5 ⁇ m-thick KAPTON EN film to prepare film C with an adhesive layer.
  • the etching rate ratio of the core insulating layer to the adhesive layer is shown in Table B3 below.
  • Thickness of core insulating Ratio of Etching rate layer total thickness of etching Core insulating layer Adhesive layer adhesive layer rate Film A with About 20 ⁇ m/min About 11 ⁇ m/min 5:2 20:11 adhesive layer Film B with About 20 ⁇ m/min About 1 ⁇ m/min 5:2 20:1 adhesive layer Film C with About 7 ⁇ m/min About 11 ⁇ m/min 5:2 7:11 adhesive layer
  • the three-layer material was dipped in a ferric chloride solution to etch the copper foil.
  • a 5 ⁇ m-thick alkali development-type dry film resist was heat laminated onto the exposed adhesive layer surface under conditions of speed 6.5 m/min, roll surface temperature 105° C., and linear pressure 2 to 4 kg/cm, and the laminate was then allowed to stand at room temperature for 15 min. Thereafter, exposure was carried out using a predetermined mask by means of a contact exposure system at 1000 mJ/cm 2 .
  • the exposed laminate was allowed to stand at room temperature for 15 min, and the dry film resist was then developed with a 1 wt % aqueous Na 2 CO 3 solution of room temperature under conditions of 30° C. and spray pressure 2 kg for 40 sec. Thereafter, the dry film resist was dried, and was dipped in an etching liquid TPE-3000 (manufactured by Toray Engineering Co., Ltd.) which had been stirred at 70° C. with a magnetic stirrer to such an extent that a vortex took place. When the polyimide film was fully removed in the form of the mask, the dry film resist was taken out of the etching liquid, followed by the separation of the dry film resist with a 3 wt % aqueous NaOH solution of 50° C. at a spray pressure of 1 kg.
  • TPE-3000 manufactured by Toray Engineering Co., Ltd.
  • FIGS. 5, 6, and 8 SEM (scanning electron microscope) photographs obtained by perspectively photographing the etching shape of the insulating layer are shown in FIGS. 5, 6, and 8 , wherein FIG. 5 shows the three-layer material using the film A with an adhesive layer, FIG. 6 the three-layer material using the film B with an adhesive layer, and FIG. 8 the three-layer material using the film C with an adhesive layer.
  • FIG. 7 is a schematic illustration of the photograph shown in FIG. 6.
  • 4 - 1 represents the upper adhesive layer
  • 4 - 2 the lower adhesive layer. Since both the adhesive layers 4 - 1 , 4 - 2 are slowly etched by the wet process, the adhesive layers are left in the form of the eaves of the roof. The core insulating layer is etched so as to be bored, and, thus, cannot be viewed at this angle.
  • 2 - 1 represents the surface of the first metal layer in its portion remaining unetched
  • 2 - 2 a vertical ridge obtained by etching of the first metal layer and shows such a state that the first metal layer has been etched on the adhesive layer 4 - 1 .
  • the second metal layer 3 remains unetched as the SUS foil.
  • the cross section of the whole film B is substantially identical as that shown in FIG. 1.
  • the laminate according to the present invention has a good shape after etching and, in the case of a continuous laminate, can be continuously etched and, even in wet etching, can be etched with high accuracy.
  • the productivity of etching is high, and the apparatus cost is also low.
  • Optimizing the etching rate of an insulating layer, constituted by a core insulating layer and an adhesive layer, in a laminate for precision electronic circuit components, such as wireless suspensions, to realize good etching shape and, in addition, rendering the adhesion of the adhesive layer good means simultaneous realization of both contradictory requirements.
  • the present invention could have realized simultaneous realization of these properties and thus has made it possible to apply wet etching, which enables continuous treatment, to laminates for precision electronic circuit components. Therefore, when the wet etching is applied, etching can be carried out in an etching time which is at least one order shorter than the etching time necessary in the conventional plasma etching.
  • a change in quality of the metal surface by etching was evaluated for a suspension wherein etching of a polyimide as an insulating layer was carried out with NF 3 plasma, a suspension wherein etching of a polyimide as an insulating layer was carried out with an alkali solution, and a stainless steel surface of the laminate before processing as a reference.
  • FIG. 3( a ) shows the laminate before processing
  • FIG. 3( b ) shows the laminate after plasma etching or wet etching with an alkali solution.
  • numeral 11 designates stainless steel
  • numeral 12 an insulating layer
  • numeral 13 copper.
  • a site indicated by an arrow A represents the surface of the stainless steel 11 of the laminate before processing
  • a site indicated by an arrow B represents the surface of the stainless steel 11 of the laminate after etching.
  • the surface of the stainless steel 11 was analyzed by XPS (X-ray photoelectron spectroscopy).
  • ESCALAB220i-XL (tradename, manufactured by VGScientific, GB) was used as an XPS analyzer.
  • X-ray was a monochromatic Al K ⁇ radiation at an output of 200 W (10 kV-20 mA).
  • the spot diameter was 1 mm ⁇
  • the lens mode was Small AreaXL 150
  • photoelectron ejection angle (ejection angle) 90 degrees.
  • the electrification neutralization is unnecessary and thus was not measured.
  • the lens mode was brought to Large Area XL, and F.O.V. and A.A. were brought to open (measuring region: 700 ⁇ m ⁇ ), and, for a silver standard sample (a 300 ⁇ m-thick silver plate having a purity of 99.98%: stock No. AG-403428, manufactured by The Nilaco Corporation), before the measurement, sputter etching with Ar + ions was carried out until the disappearance of carbon, followed by the measurement of the surface.
  • a silver standard sample a 300 ⁇ m-thick silver plate having a purity of 99.98%: stock No. AG-403428, manufactured by The Nilaco Corporation
  • the range of 0 to 1100 eV was measured at intervals of 1.0 eV (1101 points in total).
  • P.E. pass energy
  • the number of scans was a desired one.
  • the narrow scan spectrum basically, the range of ⁇ 10 eV around the position of the main peak of the element detected in the wide area was measured at intervals of 0.100 eV (201 points in total). In this case, P.E. was 20 eV, and the number of scans was a desired one.
  • FIG. 9 is an XPS chart of the dry etching sample
  • FIGS. 10 and 11 are XPS charts showing detailed measured data of portions corresponding respectively to nitrogen and fluorine.
  • the measurement results of the wet etching sample are shown as XPS charts in FIGS. 12, 13, and 14 .
  • FIG. 15 For XPS charts of the references, an XPS chart for the plasma etching sample is shown in FIG. 15, and an XPS chart for the wet etching sample is shown in FIG. 16.
  • the organic nitride and the organic fluoride detected in both the dry etching sample and the wet etching sample are estimated to be a very small amount of the polyimide left after etching and organic matter deposited during the process.

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  • Laminated Bodies (AREA)
  • Adjustment Of The Magnetic Head Position Track Following On Tapes (AREA)
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  • Insulating Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)
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US20060127685A1 (en) * 2003-02-18 2006-06-15 Mitsui Chemicals, Inc. Layered polyimide/metal product
US20080089072A1 (en) * 2006-10-11 2008-04-17 Alti-Electronics Co., Ltd. High Power Light Emitting Diode Package
US20080225438A1 (en) * 2005-03-03 2008-09-18 Nippon Steel Chemical Co., Ltd Laminate for Suspension and Method for Producing Same
US20160167358A1 (en) * 2014-12-12 2016-06-16 Micro Materials Inc. Support for bonding a workpiece and method thereof

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JP2006244599A (ja) * 2005-03-03 2006-09-14 Nippon Steel Chem Co Ltd サスペンション用積層体およびその製造方法
DE102009012827A1 (de) * 2009-03-03 2010-10-07 Gebr. Schmid Gmbh & Co. Verfahren zur Texturierung von Siliziumwafern für Solarzellen und Behandlungsflüssigkeit dafür
TWI396482B (zh) * 2010-07-30 2013-05-11 Optromax Electronics Co Ltd 線路基板製程及線路基板結構
TWI521016B (zh) 2012-07-18 2016-02-11 財團法人工業技術研究院 蝕刻含聚亞醯胺之膜層的方法
US10149394B2 (en) * 2014-01-22 2018-12-04 Ube Industries, Ltd. Method for forming conductor layer, and method for producing multilayer wiring substrate using same
EP3146560A4 (en) * 2014-05-23 2018-04-18 Materion Corporation Air cavity package
JP6973476B2 (ja) * 2017-04-06 2021-12-01 大日本印刷株式会社 ポリイミドフィルム、積層体、及びディスプレイ用表面材
JP7088173B2 (ja) * 2017-04-10 2022-06-21 大日本印刷株式会社 フレキシブルディスプレイ用表面材

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US20080225438A1 (en) * 2005-03-03 2008-09-18 Nippon Steel Chemical Co., Ltd Laminate for Suspension and Method for Producing Same
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US20160167358A1 (en) * 2014-12-12 2016-06-16 Micro Materials Inc. Support for bonding a workpiece and method thereof
US11097306B2 (en) * 2014-12-12 2021-08-24 Micro Materials Inc. Support for bonding a workpiece and method thereof

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