WO2010041510A1 - Stratifié flexible enduit de conducteur, carte de circuit imprimé flexible pour cof, et procédés de fabrication associés - Google Patents

Stratifié flexible enduit de conducteur, carte de circuit imprimé flexible pour cof, et procédés de fabrication associés Download PDF

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Publication number
WO2010041510A1
WO2010041510A1 PCT/JP2009/063816 JP2009063816W WO2010041510A1 WO 2010041510 A1 WO2010041510 A1 WO 2010041510A1 JP 2009063816 W JP2009063816 W JP 2009063816W WO 2010041510 A1 WO2010041510 A1 WO 2010041510A1
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WIPO (PCT)
Prior art keywords
layer
heat
clad laminate
resistant resin
conductor layer
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PCT/JP2009/063816
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English (en)
Japanese (ja)
Inventor
佐藤　哲朗
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三井金属鉱業株式会社
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Publication of WO2010041510A1 publication Critical patent/WO2010041510A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/4985—Flexible insulating substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • H05K1/0393—Flexible materials
    • 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
    • H05K2201/0191—Dielectric layers wherein the thickness of the dielectric plays an important role

Definitions

  • the present invention relates to a flexible conductor layer-clad laminate that can be used for a COF flexible printed wiring board on which electronic components such as ICs or LSIs are mounted, a COF flexible printed wiring board using the same, and a method of manufacturing the same.
  • the COF flexible printed wiring board used for this COF does not have a device hole, a flexible conductor layer-clad laminate in which a conductor layer and an insulating layer are laminated in advance is used, and the insulating layer generally has a thickness. This is because a polyimide film with a thickness of 30 to 40 ⁇ m is used. If the thickness is less than 30 ⁇ m, there is a risk of causing problems when transporting sprockets in the manufacturing process of COF flexible printed wiring boards and COF mounting processes due to insufficient mechanical strength. On the other hand, if it is thicker than 40 ⁇ m, it causes a conveyance failure during mounting due to a phenomenon called springback.
  • the present invention is a flexible conductive layer-clad laminate and a flexible COF that can be manufactured at a relatively low cost without causing a problem of terminal sinking or a springback problem when mounting an IC chip. It aims at providing a printed wiring board and these manufacturing methods.
  • a first aspect of the present invention that solves the above-mentioned problems is that a first heat-resistant resin layer having a thickness of 1 to 10 ⁇ m made of a heat-resistant resin having a glass transition temperature of 320 ° C. or higher is formed on one surface of a conductor layer, and thermosetting.
  • a thermosetting resin layer having a thickness of 4 to 10 ⁇ m made of a resin composition and a second heat resistant resin layer having a thickness of 10 to 35 ⁇ m made of a heat resistant resin having a glass transition temperature of 300 ° C. or higher are sequentially provided.
  • the flexible conductor layer-clad laminate is characterized.
  • the first heat resistant resin prevents the IC chip terminal from sinking and the low elastic resin layer is provided, so that the problem of springback is also solved. Is done. Moreover, since it can manufacture by a lamination, cost reduction can be achieved.
  • the thermosetting resin composition contains a thermosetting resin by a thermosetting reaction that does not release by-products.
  • the flexible conductor layer-clad laminate is characterized.
  • thermosetting resin layer is formed of a thermosetting resin that does not release by-products from the thermosetting reaction, the laminate is free from problems such as blistering.
  • the thermosetting resin composition in the flexible conductor layer-clad laminate according to the first or second aspect, includes an aromatic polyamide resin polymer and an epoxy resin. Located on flexible conductor layered laminate.
  • thermosetting resin layer also serves as an adhesive layer, a laminate that is favorably bonded by lamination can be obtained.
  • the flexible conductor layer-clad laminate in the flexible conductor layer-clad laminate according to any one of the first to third aspects, the first heat-resistant resin layer, the thermosetting resin layer, and the second heat-resistant resin layer.
  • the flexible conductor layer-clad laminate is characterized in that the insulating layer comprising the resin layer has a thickness of 30 to 40 ⁇ m.
  • a laminate having a thickness suitable as a base material for COF is obtained.
  • the conductor layer is made of copper foil. is there.
  • a copper clad laminate suitable as a COF base material is obtained.
  • a laminate of the conductor layer and the first heat-resistant resin layer, and the second heat-resistant resin layer are provided.
  • a flexible conductor layer-clad laminate is obtained by laminating a resin layer via the thermosetting resin layer.
  • the sixth aspect it can be manufactured by laminating two layers, and can be manufactured relatively easily and at low cost.
  • a seventh aspect of the present invention is formed by using the flexible conductor layer-clad laminate described in any one of the first to sixth aspects, and is formed by patterning the conductor layer and mounting a semiconductor chip.
  • the first heat-resistant resin layer prevents the IC chip terminals from sinking and the low-elasticity resin layer is provided, the problem of springback is also solved. Moreover, since it can manufacture by a lamination, cost reduction can be achieved.
  • the eighth aspect of the present invention comprises a first heat-resistant resin layer having a thickness of 1 to 10 ⁇ m made of a heat-resistant resin having a glass transition temperature of 320 ° C. or higher on one surface of a conductor layer, and a thermosetting resin composition.
  • a flexible conductor layer-clad laminate comprising a thermosetting resin layer having a thickness of 4 to 10 ⁇ m and a second heat resistant resin layer having a thickness of 10 to 35 ⁇ m made of a heat resistant resin having a glass transition temperature of 300 ° C. or higher.
  • a manufacturing method comprising applying a heat-resistant resin precursor coating solution having a glass transition temperature of 300 ° C.
  • thermosetting resin composition A flexible conductor layer-clad laminate obtained by laminating the laminate and the heat-resistant resin film via the thermosetting resin composition, and It is in the manufacturing method.
  • the first heat resistant resin layer when the first heat resistant resin layer is formed by a coating method and laminated through the second heat resistant resin layer and the low elastic resin layer, the first heat resistant resin layer is obtained. Since the resin layer prevents the terminal of the IC chip from sinking and the low-elasticity resin layer is provided, a flexible conductor layer-clad laminate that can eliminate the problem of springback can be manufactured relatively easily and at low cost.
  • thermosetting resin layer does not release by-products during the thermosetting reaction.
  • thermosetting resin layer is formed of a thermosetting resin that does not release by-products from the thermosetting reaction, a laminate without problems such as blistering can be manufactured.
  • the thermosetting resin layer includes an aromatic polyamide resin polymer and an epoxy resin. It is in the manufacturing method of the flexible conductor layer tension laminated board characterized by consisting of.
  • the low elastic resin layer also serves as the adhesive layer, it is possible to obtain a laminated plate that is satisfactorily bonded by lamination.
  • the first heat-resistant resin layer, the thermosetting resin layer, A method for producing a flexible conductor layer-clad laminate is characterized in that a flexible conductor layer-clad laminate having a thickness of 30 to 40 ⁇ m of an insulating layer comprising a second heat-resistant resin layer is produced.
  • a laminate having a thickness suitable as a COF substrate is produced.
  • a copper foil or a copper foil with a carrier is used as the conductor layer.
  • the method for producing a flexible conductor layer-clad laminate is not limited to any one of the eighth to eleventh aspects.
  • a copper-clad laminate suitable as a substrate for COF is relatively easily manufactured by forming and laminating a first heat-resistant resin layer using a copper foil or a copper foil with a carrier.
  • a flexible printed wiring board for COF is produced from a flexible conductor layer-clad laminate obtained by the method for producing a flexible conductor layer-clad laminate described in any one of the eighth to twelfth aspects. This is a method for producing a flexible printed wiring board for COF.
  • the first heat-resistant resin layer prevents the terminal of the IC chip from sinking and the low-elasticity resin layer is also used as the adhesive layer, the problem of springback is also eliminated.
  • a flexible printed wiring board is manufactured.
  • FIG. 1 is a schematic cross-sectional view of a flexible conductor layer-clad laminate of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing the production process of the flexible conductor layer-clad laminate of the present invention.
  • FIG. 1 shows a flexible conductor layered laminate according to an embodiment.
  • the flexible conductor layer-clad laminate 10 of this embodiment includes a conductor layer 11 made of metal foil, a first heat-resistant resin layer 12, a thermosetting resin layer 13, and a second heat-resistant resin layer 14. It has the laminated structure.
  • the metal foil is not particularly limited as long as it has a thickness and quality that can be used as a flexible printed wiring board for COF. Generally, a thickness of about 5 to 35 ⁇ m is used. Further, from the viewpoint of handling in the manufacturing process, a metal foil with a carrier may be used in the manufacturing process, and the carrier may be finally removed.
  • examples of the metal foil include copper foil and aluminum foil
  • examples of the carrier include copper foil and aluminum foil.
  • the first heat-resistant resin layer is made of a heat-resistant resin having a glass transition temperature of 320 ° C. or higher, and has a thickness of 1 to 10 ⁇ m, preferably 3 to 6 ⁇ m.
  • the connection terminal of the IC chip is submerged when COF mounting is performed. It has been found that it can be effectively prevented, and has such a configuration.
  • Examples of the heat resistant resin for forming the first heat resistant resin layer include a polyimide resin and a polyamideimide resin.
  • a resin provided on the conductor foil by a coating method is preferable, and particularly preferable is a resin that becomes a heat-resistant resin layer by applying a heat-resistant resin precursor composition and then curing.
  • the first heat-resistant resin layer has a volatile component contained before lamination of 2% by mass or less, preferably 1% by mass or less. This is because the first heat-resistant resin layer is placed at a position in direct contact with the metal foil, and the amount of residual volatile components such as solvents is strictly controlled to prevent the sinking when mounting the IC chip. It is to do. In other words, if the volatile component remains in the first heat resistant resin layer in excess of 2% by mass, the plasticity of the volatile component such as a solvent causes a decrease in the elastic modulus at a high temperature of the heat resistant resin layer. This is because even if a heat-resistant resin having a glass transition temperature of 320 ° C. or higher is used, its original performance is not exhibited, and there is a high possibility that subsidence easily occurs.
  • the second heat-resistant resin layer is made of a heat-resistant resin having a glass transition temperature of 300 ° C. or higher and has a thickness of 10 to 35 ⁇ m, preferably 20 to 30 ⁇ m.
  • the second heat-resistant resin layer is preferably manufactured as a heat-resistant resin film in terms of cost and handling.
  • a polyimide-based film or a polyamide-imide-based film that is commercially available as a base material for flexible printed wiring boards is used. It is preferable to use it.
  • the second heat-resistant resin layer When the second heat-resistant resin layer is thin, handling becomes difficult and wrinkles are easily generated during lamination. When the second heat-resistant resin layer is thick, the thickness of the low-elasticity resin layer is relatively thin due to the total thickness. Both are undesirable. From such a viewpoint and easy availability and cost, it is preferable to use a polyimide film having a thickness of 25 ⁇ m.
  • wholly aromatic polyimides obtained by polymerization of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether (for example, trade name: Kapton EN; manufactured by Toray DuPont) and biphenyltetracarboxylic acid-2 anhydride
  • Kapton EN for example, trade name: Kapton EN; manufactured by Toray DuPont
  • PPD paraphenylenediamine
  • Upilex S manufactured by Ube Industries
  • Kaneka apical (manufactured by Kaneka), and the like.
  • the reason why the glass transition temperature of the second heat resistant resin layer is set to 300 ° C. or more is to maintain heat resistance against connection with solder having a melting point of 288 ° C.
  • the thermosetting resin layer is made of a thermosetting resin composition and has a thickness of 4 to 10 ⁇ m, preferably 5 to 8 ⁇ m.
  • the thermosetting resin layer preferably has a low elastic modulus, for example, a room temperature elastic modulus of 3 GPa or less, preferably 1.5 to 2.5 GPa, more preferably about 1.5 to 2 GPa. It is. It has been found that even if such a low elastic resin layer having a low elastic modulus is provided, there is no adverse effect on the sinking when the IC chip is mounted, and spring back can be effectively prevented.
  • a room temperature elastic modulus for example, a room temperature elastic modulus of 3 GPa or less, preferably 1.5 to 2.5 GPa, more preferably about 1.5 to 2 GPa. It is. It has been found that even if such a low elastic resin layer having a low elastic modulus is provided, there is no adverse effect on the sinking when the IC chip is mounted, and spring back can be effectively prevented.
  • thermosetting resin layer is preferably one that can be formed by a coating method and that functions as an adhesive layer.
  • thermosetting resin layer need not strictly define the volatile components contained before lamination. That is, if the content of the volatile component of the thermosetting resin layer does not show stickiness at room temperature and does not cause any problems in handling after coating, it contains more than 2% by mass of volatile components. May be.
  • a volatile component such as a solvent
  • the volatile component contained in the thermosetting resin layer can be easily removed after lamination, and can be removed in a short time by heating performed at the time of curing the thermosetting resin layer after lamination. .
  • thermosetting resin may be sufficiently removed before lamination.
  • the thermosetting resin is easily softened and exhibits fluidity before curing, and lamination by lamination can be performed without any problem.
  • thermosetting resin composition containing a thermosetting resin that is cured by a thermosetting reaction that does not generate by-products such as water and gas.
  • the by-product during the thermosetting can be completely removed from the layer sandwiched between the first heat-resistant resin layer and the second heat-resistant resin layer after lamination. It is extremely difficult.
  • the removal of volatile components such as solvents can be gradually performed by heating the temperature near the boiling point of the volatile components, but by-products due to the curing reaction occur after the reaction occurs above a predetermined temperature. This is because it suddenly occurs when the temperature at which the reaction starts is exceeded, causing bubble accumulation called voids and delamination between layers.
  • the solvent such as methyl ethyl ketone and cyclopentanone contained in the thermosetting resin composition of the present invention has a boiling point as low as 150 ° C. or less and is heated at 150 ° C. to 230 ° C., which is the curing temperature of the thermosetting resin. Since it gradually evaporates while it is gradually heated to the atmosphere, it can be easily removed without providing a new removal step.
  • polyamic acid which is a precursor of polyimide resin
  • the ring closing reaction of polyamic acid requires a temperature of 300 ° C. or higher. When heated further, water molecules are rapidly generated due to dehydration reaction, and it is extremely difficult to suppress the occurrence of swelling and voids associated therewith.
  • thermosetting resin composition an organic solvent-soluble thermosetting resin that cures by a thermosetting reaction that does not generate by-products such as water and gas, an organic solvent-soluble base resin,
  • curing agent and an organic solvent can be mentioned.
  • thermosetting resins that are cured by a thermosetting reaction that does not generate by-products such as water and gas are excluded from those due to dehydration reaction type, decarboxylation reaction, deformalin reaction, etc. And novolak type phenol resins.
  • examples of the base resin include aromatic polyamide resin polymers. This is because a thermosetting resin layer having good compatibility with the thermosetting resin and having a low elastic modulus and good adhesiveness can be formed.
  • the aromatic polyamide resin polymer can include a composition containing a thermosetting resin made of an epoxy resin.
  • the aromatic polyamide resin polymer The resin composition which consists of a hardening accelerator which is soluble in an epoxy resin, a hardening
  • the “aromatic polyamide resin polymer” is obtained by reacting an aromatic polyamide resin and a rubber resin.
  • the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid.
  • the aromatic diamine it is preferable to use 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like.
  • the dicarboxylic acid it is preferable to use phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like.
  • 4-hydroxyisophthalic acid may be used for the purpose of providing a crosslinking point with the epoxy resin.
  • the rubbery resin to be reacted with the aromatic polyamide resin must be copolymerized with the aromatic polyamide resin and incorporated into the molecule, and particularly represented by CTBN (carboxy group-terminated butadiene nitrile), A rubber component having a carboxyl group at the end of the molecule is used.
  • the aromatic polyamide resin and rubber resin that constitute the aromatic polyamide resin polymer are preferably used in a blend of 25 wt% to 75 wt% of the aromatic polyamide resin and the remaining rubber resin.
  • the aromatic polyamide resin is less than 25 wt%, the abundance ratio of the rubber component becomes too high and the heat resistance is inferior.
  • the aromatic polyamide resin becomes too large and curing occurs. Later hardness becomes too high and becomes brittle.
  • This aromatic polyamide resin polymer is used for the purpose of reducing damage caused by an etching solution when etching a conductor layer after being processed into a conductor layer-clad laminate.
  • This aromatic polyamide resin polymer is required to be soluble in a solvent.
  • This aromatic polyamide resin polymer is used in a blending ratio of 20 to 80 parts by weight.
  • the “epoxy resin” is one having two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. It is preferable to use a polyfunctional solid epoxy resin (hereinafter referred to as a polyfunctional solid epoxy resin) containing three or more epoxy groups per molecule and solid at room temperature with a softening point of 50 ° C. or higher.
  • a polyfunctional solid epoxy resin containing three or more epoxy groups per molecule and solid at room temperature with a softening point of 50 ° C. or higher.
  • examples of such polyfunctional solid epoxy resins include novolak type epoxy resins, o-cresol novolak type epoxy resins, triglycidyl isocyanurate, tetrakis (glycidyloxyphenyl) ethane, and the like. These polyfunctional solid epoxy resins may be used alone or in combination of two or more.
  • liquid epoxy resin an epoxy resin that is liquid at room temperature
  • a liquid epoxy resin refers to an epoxy resin having fluidity at room temperature without adding a solvent.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, epoxidized polybutadiene, and N, N diglycidyl aniline.
  • glycidylamine compounds such as polyglycidyl esters of organic polycarboxylic acids such as tetrahydrophthalic acid diglycidyl ester, and cyclic aliphatic epoxy resins.
  • liquid epoxy resins include those that have high crystallinity and that, by themselves, crystallize at room temperature and become powdery. These liquid epoxy resins may be used alone or in combination of two or more.
  • the epoxy resin containing the liquid epoxy resin is added as an epoxy resin blend in which a curing agent and a curing accelerator added as necessary are blended.
  • the epoxy resin curing agent is known as a phenol resin, an acid anhydride, or a polyamine compound, but is not particularly limited as long as it is used as a material for an electronic component.
  • generally known tertiary amines, imidazoles, urea compounds and the like are used as curing accelerators added as necessary.
  • a preferable blending ratio of each of these components in a suitable thermosetting resin composition is 20 to 80% by weight of the base resin, more preferably 30 to 70% by weight in a total of 100% by weight of the base resin and the epoxy resin blend.
  • the epoxy resin composition is 20 to 80% by mass, more preferably 40 to 70% by mass.
  • the preferable blending ratio of the liquid epoxy resin is 5 to 80 parts by mass, more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyfunctional solid epoxy resin.
  • the blending ratio of the liquid epoxy resin is less than 5 parts by mass, the effect of improving the fluidity is not remarkable, and when it exceeds 80 parts by mass, the solder heat resistance tends to decrease.
  • thermosetting resin composition contains an epoxy resin
  • it can be applied as a varnish and then dried to form an uncured thermosetting resin layer.
  • the uncured thermosetting resin layer before laminating is dried in a state where the volatile component contained is 2% by mass or less, preferably 1% by mass or less. This is to prevent the volatile component from volatilizing and remaining between the layers during the subsequent thermosetting process.
  • thermosetting resin layer After laminating in this way, after being wound on a roll, the uncured thermosetting resin layer is cured by heating at a higher temperature than the laminating step to obtain a thermosetting resin layer.
  • the lamination temperature can be, for example, 100 ° C. to 200 ° C., preferably 100 ° C. to 150 ° C., and the thermosetting temperature can be 150 ° C. to 230 ° C.
  • thermosetting resin composition can be applied to the second heat-resistant resin layer or the first heat-resistant resin layer, but is preferably applied to the second heat-resistant resin layer.
  • FIG. 2 shows an example of a method for producing a flexible conductor layered laminate according to the present invention.
  • FIG. 2A shows a state in which the first heat-resistant resin layer 12 is provided on the conductor layer 11 while the uncured thermosetting resin layer 13 a is provided on the second heat-resistant resin layer 14. Next, these are laminated to form a laminate, and the uncured thermosetting resin layer 13a is cured to form the thermosetting resin layer 13, whereby the flexible conductor layer-clad laminate 10 shown in FIG. Can be obtained.
  • the flexible conductor layer-clad laminate 10 can be a COF flexible printed wiring board by a predetermined process. That is, after forming the flexible copper-clad laminate 10 into a tape shape having a predetermined width as necessary, a sprocket hole is formed, for example, the conductor layer 11 is patterned by a photolithography process to form a predetermined circuit, and for COF It can be set as a flexible printed wiring board.
  • Such a flexible printed wiring board for COF prevents the sinking of the terminals of the IC chip when mounting the IC chip or the like, and also eliminates the problem of conveyance failure during mounting due to springback. It is.
  • the method disclosed in the examples of JP-A-2007-204714 was employed.
  • the Tg of the polyamideimide resin to be synthesized can be freely set from about 300 ° C. to about 400 ° C. by changing the ratio of the monomer components.
  • Each polyamideimide resin 1 to 3 was an N-methylpyrrolidone solution having a solid content of 10%.
  • the glass transition temperature Tg of each polyamideimide resin was as follows using the polyamideimide resin film prepared as follows.
  • the polyamide-imide resin varnish after completion of the synthesis reaction was applied on an aluminum plate using a bar coder so that the thickness after drying was 25 ⁇ m. Subsequently, as primary drying, it was dried in a hot air dryer at 150 ° C. for 10 minutes, and as secondary drying, it was heated at 350 ° C. in a nitrogen atmosphere for 30 minutes. Next, the aluminum plate was removed by etching using a 10% caustic soda solution, washed with water, and dried to obtain a polyamideimide resin film.
  • the dynamic viscoelasticity of the polyamideimide resin film was measured, and the peak value of tan ⁇ was defined as Tg.
  • Example 1 Polyamide that forms a polyamide-imide resin layer with a glass transition temperature of 395 ° C. on the base material surface (glossy surface) of a commercially available electrolytic copper foil with a thickness of 15 ⁇ m (NA-DFF: trade name, manufactured by Mitsui Kinzoku Mining Co., Ltd.)
  • the imide resin varnish was applied using a bar coater so that the thickness after primary drying was 6 ⁇ m. After coating, during hot air drying, primary drying is performed at 150 ° C. for 10 minutes, followed by secondary drying at 350 ° C. for 30 minutes in a nitrogen atmosphere, and a copper-clad laminate composed of a copper foil and a polyamideimide layer A plate was formed.
  • the residual amount of volatile components in the copper clad laminate was 0.5% by mass.
  • Volatile component residual amount (%) [(W 0 ⁇ W 1 ) / (W 0 ⁇ W Cu )] ⁇ 100
  • W 0 Mass of copper-clad laminate before heating
  • W 1 Mass of copper-clad laminate after heating at 350 ° C. for 15 minutes under vacuum
  • W 2 Copper-clad after heating for 15 minutes at 350 ° C. under vacuum Mass after etching away copper foil of laminate
  • W Cu Mass of copper foil (W 1 -W 2 )
  • thermosetting resin composition prepared as described below was applied to one side of a commercially available polyimide film with a thickness of 25 ⁇ m, Upilex S (trade name, manufactured by Ube Industries), dried, and uncured thermoset. A laminated board having a conductive resin layer was obtained. The coating thickness at this time was 6 ⁇ m after heating at 150 ° C. for 3 minutes.
  • the remaining amount of volatile components in the laminated board was 4.5% by mass.
  • Volatile component residual amount (%) [(W 10 ⁇ W 11 ) / (W 10 ⁇ W f )] ⁇ 100
  • W 10 mass of the laminate before heating (100 mm ⁇ 100 mm)
  • W 11 Mass of laminate after heating for 60 minutes at 200 ° C. under atmospheric pressure
  • W f 10-point average weight of S of Iupilex (100 mm ⁇ 100 mm)
  • thermosetting resin composition was prepared as follows.
  • thermosetting resin composition was prepared by adding methyl ethyl ketone thereto to a resin solid content of 30% by mass.
  • the above-described copper-clad laminate and the laminate were laminated using a laminating apparatus so that the polyamideimide layer and the uncured thermosetting resin layer face each other.
  • the laminating conditions at this time are as follows. There was no generation of wrinkles or entrainment of bubbles during lamination.
  • the laminated body thus laminated was wound with dust-free paper in between and heated in the atmosphere to thermally cure the uncured thermosetting resin layer, thereby obtaining a flexible conductor layer-clad laminate of this example.
  • the reason why the dust-free paper is sandwiched is to prevent the laminates from completely adhering to each other, and to completely remove the residual solvent simultaneously with the curing of the thermosetting resin in the thermosetting process. It is.
  • thermosetting conditions were such that the temperature was raised from room temperature to 190 ° C. over 4 hours and held at 190 ° C. for 4 hours. After the holding time, the power was turned off and the mixture was gradually cooled.
  • Example 2 A flexible copper-clad laminate was obtained in the same manner as in Example 1 except that the thickness of the polyamideimide resin layer in Example 1 was 3 ⁇ m.
  • Example 3 A flexible copper-clad laminate was obtained in the same manner as in Example 1 except that the thickness of the polyamideimide resin layer in Example 1 was 1 ⁇ m.
  • Example 4 A flexible copper clad laminate was obtained in the same manner as in Example 1 except that the polyamideimide resin 2 was used in place of the polyamideimide resin 1 in Example 1.
  • Example 5 A flexible copper clad laminate was obtained in the same manner as in Example 1 except that the thickness of the uncured thermosetting resin in Example 1 was 10 ⁇ m.
  • Example 6 A flexible copper-clad laminate was obtained in the same manner as in Example 1 except that the thickness of the uncured thermosetting resin in Example 1 was 4 ⁇ m.
  • Example 1 A flexible copper-clad laminate was obtained in the same manner as in Example 1 except that the thickness of the polyamideimide resin layer in Example 1 was 0.5 ⁇ m.
  • Example 2 A flexible copper-clad laminate was obtained in the same manner as in Example 1 except that the thickness of the uncured thermosetting resin in Example 1 was 15 ⁇ m.
  • Example 3 A flexible copper clad laminate was obtained in the same manner as in Example 1 except that the thickness of the uncured thermosetting resin in Example 1 was 2 ⁇ m.
  • Example 4 A flexible copper clad laminate was obtained in the same manner as in Example 1 except that the polyamideimide resin 3 was used instead of the polyamideimide resin 1 in Example 1.
  • Test example A test board for evaluation of “terminal sinking” was obtained by forming a predetermined circuit on the flexible copper-clad laminates of Examples 1 to 6 and Comparative Examples 1 to 4 and then performing tin plating on the inner lead portion. .
  • the “terminal sinking” evaluation is performed by mounting an IC having a gold bump on the test substrate, observing a cross section of the terminal portion after the mounting is completed, and determining that the sinking amount exceeds 3 ⁇ m. The case of 3 ⁇ m or less was performed by judging as good “ ⁇ ”.
  • a flip chip bonder TFC-3000 manufactured by Shibaura Mechatronics
  • the bonding head tool temperature is 400 ° C.
  • the stage temperature is 100 ° C.
  • the bonding pressure is 20 gf per bump. Set and went.
  • Example 3 where the thickness of the first heat-resistant resin layer was 1 ⁇ m.
  • Tg of 1st heat resistant resin prevented terminal sinking in Example 4 of 325 degreeC, it turned out that terminal sinking becomes large in the comparative example 4 whose Tg is 308 degreeC.
  • a heat resistant resin having a Tg of 320 ° C. or higher may be used.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un stratifié flexible enduit de conducteur qui comprend séquentiellement, sur un côté d’une couche de conducteur (11), une première couche de résine thermorésistante (12) qui possède une épaisseur de 1 à 10 μm et se compose d’une résine thermorésistante ayant une température de transition vitreuse non inférieure à 320 °C ; une couche de résine thermodurcissable (13) qui possède une épaisseur de 4 à 10 μm et se compose d’une composition de résine thermodurcissable ; et une seconde couche de résine thermorésistante (14) qui possède une épaisseur de 10 à 35 μm et se compose d’une résine thermorésistante ayant une température de transition vitreuse non inférieure à 300 °C.
PCT/JP2009/063816 2008-10-07 2009-08-04 Stratifié flexible enduit de conducteur, carte de circuit imprimé flexible pour cof, et procédés de fabrication associés WO2010041510A1 (fr)

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JP2008261108 2008-10-07

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TWI461293B (zh) * 2011-11-29 2014-11-21 Microcosm Technology Co Ltd Composite laminated board and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006013135A (ja) * 2004-06-25 2006-01-12 Furukawa Electric Co Ltd:The フレキシブルプリント回路基板用積層体及びフレキシブルプリント回路基板
JP2007115722A (ja) * 2005-10-17 2007-05-10 Tdk Corp 可撓性配線板及び電子部品

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006013135A (ja) * 2004-06-25 2006-01-12 Furukawa Electric Co Ltd:The フレキシブルプリント回路基板用積層体及びフレキシブルプリント回路基板
JP2007115722A (ja) * 2005-10-17 2007-05-10 Tdk Corp 可撓性配線板及び電子部品

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