WO2015099451A1 - Feuille de résine isolante pour la formation d'une carte de circuit imprimé souple, son procédé de fabrication et carte de circuit imprimé la comprenant - Google Patents

Feuille de résine isolante pour la formation d'une carte de circuit imprimé souple, son procédé de fabrication et carte de circuit imprimé la comprenant Download PDF

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Publication number
WO2015099451A1
WO2015099451A1 PCT/KR2014/012815 KR2014012815W WO2015099451A1 WO 2015099451 A1 WO2015099451 A1 WO 2015099451A1 KR 2014012815 W KR2014012815 W KR 2014012815W WO 2015099451 A1 WO2015099451 A1 WO 2015099451A1
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layer
resin sheet
epoxy
printed circuit
circuit board
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PCT/KR2014/012815
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English (en)
Korean (ko)
Inventor
유의덕
김인욱
박광석
정수임
김형규
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주식회사 두산
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Publication of WO2015099451A1 publication Critical patent/WO2015099451A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • 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
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • 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
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1152—Replicating the surface structure of a sacrificial layer, e.g. for roughening

Definitions

  • the present invention provides an insulation resin sheet for forming an insulation layer of a build-up printed circuit board and a method for manufacturing the same, which may achieve high density microcircuit pattern, good adhesion and moisture absorption and heat resistance at the same time, including the insulation resin sheet as an insulation layer. It relates to a flexible printed circuit board and a method of manufacturing the same.
  • a film manufactured through a sputtering method and a chemical etching method may be used as a material for implementing a conventional microcircuit.
  • the sputtering method deposits a metal thin film on an untreated (or dry plasma treated) polyimide film through a sputter process, and a pattern through a semi-additive process on a metal thin film formed through the process. It is a method of implementing microcircuits by plating. In this case, only the intermolecular force is acting between the resin material constituting the substrate and the metal thin film layer, so that initial adhesion can be secured, but the problem of deterioration of adhesion, which is the core of the technology, is caused by thermal shock and chemical resistance.
  • Another method, chemical etching is to form a surface roughness through the selective etching of the Smearing Material in the insulating layer resin material to form a metal thin film through electroless copper plating.
  • the metal thin film formed through the above process is plated through a semi-additive process to implement a microcircuit.
  • the surface roughness of the film can be freely controlled through selective etching.
  • polyimide there is a problem in that the chemical resistance of the resin material, which is an insulating layer, is weakened when the roughness is formed.
  • the interlayer adhesion between the substrates was poor and not satisfactory in terms of hygroscopic heat resistance characteristics.
  • the present invention has been made to solve the above problems of the conventional microcircuit method, and after forming an epoxy insulating layer and a thermoplastic polyimide layer on the polyimide film sequentially, and then a specific roughness on the surface of the thermoplastic polyimide By forming, to implement a fine circuit pattern implementation technology and high adhesion at the same time.
  • an object of the present invention is to provide an insulating resin sheet having a novel laminated structure capable of simultaneously exhibiting a fine circuit pattern and exhibiting good adhesion and moisture absorption heat resistance characteristics while solving problems of the conventional microcircuit method.
  • the present invention includes a flexible printed circuit board and a method for manufacturing the same by including an insulating layer formed by using the insulating resin sheet, which can reduce defects in the process of forming a circuit and simultaneously improve interlayer adhesion strength, heat resistance and long-term reliability. Another purpose is to provide.
  • the present invention is a polyimide film; An epoxy insulating layer formed on one or both surfaces of the polyimide film; And an insulating resin sheet for forming a flexible printed circuit board (FPCB) formed on the epoxy insulating layer and including a thermoplastic polyimide (TPI) film layer having a predetermined surface roughness.
  • FPCB flexible printed circuit board
  • TPI thermoplastic polyimide
  • the epoxy insulating layer comprises: (a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400-1000 g / eq; (b) low equivalent second epoxy resins having an epoxy equivalent weight (EEW) in the range of 100-300 g / eq; (c) dimer acid-modified epoxy resins; (d) benzoxazine resins; And (e) two or more curing agents, wherein at least one of the first epoxy resin and the second epoxy resin is formed by curing a thermosetting resin composition having a polydispersity index (PDI) of 2 or less.
  • PDI polydispersity index
  • the surface roughness (Ra) of the thermoplastic polyimide layer is preferably in the range of 0.2 to 3.0 ⁇ m
  • the thermoplastic polyimide layer may be polyimide, polyamide, polyamideimide, and polyamic acid. It may be formed by applying a liquid composition and then curing the resin composition comprising at least one resin selected from the group consisting of resins.
  • the thickness of the polyimide film is in the range of 5 ⁇ m to 100 ⁇ m
  • the thickness of the epoxy insulating layer is in the range of 1 ⁇ m to 50 ⁇ m
  • the thickness of the thermoplastic polyimide layer is in the range of 1 ⁇ m to 50 ⁇ m.
  • a support layer may be further included on the thermoplastic polyimide layer, and may further include a release layer between the thermoplastic polyimide layer and the support layer.
  • the present invention is the above-mentioned insulating resin sheet; And a copper foil layer formed on the upper and lower surfaces of the thermoplastic polyimide layer of the insulating resin sheet, respectively.
  • the present invention is the above-mentioned insulating resin sheet; Copper foil plating layers respectively formed on the upper and lower surfaces of the thermoplastic polyimide layer of the said insulated resin sheet, and have a predetermined pattern; And a plurality of through holes provided to penetrate the insulating resin sheet and plated to electrically connect patterns of copper foil plating layers respectively formed on upper and lower surfaces thereof.
  • this invention provides the manufacturing method of the above-mentioned insulating resin sheet.
  • the manufacturing method comprises the steps of (i) coating an epoxy insulating layer forming thermosetting resin composition on one or both surfaces of the polyimide film and drying to form an epoxy insulating layer; (ii) coating a composition for forming a thermoplastic polyimide layer on the epoxy insulating layer and then drying to form a thermoplastic polyimide layer; And (iii) laminating the polyimide film and the copper foil having a predetermined surface roughness, wherein the thermoplastic polyimide layer of the polyimide film and the surface roughness surface of the copper foil are disposed to be in contact with each other, and then heated and pressurized onto the surface of the thermoplastic polyimide layer. And transferring the surface roughness surface of the copper foil.
  • the present invention provides a method of manufacturing a flexible printed circuit board using the above-described insulating resin sheet.
  • the manufacturing method includes the steps of (I) forming one or more holes in the above-mentioned insulating resin sheet; (II) desmearing the surface of the insulating resin sheet and the inside of the hole to form roughness; (III) forming an electroless plating layer on the roughness surface and the inner surface of the hole of the insulating resin sheet; (IV) forming a pattern using a photoresist on the formed electroless plating layer; (V) forming a circuit layer by electroplating on the pattern; And (VI) exfoliating the photoresist and removing the exposed electroless plating layer.
  • the present invention provides a polyimide film capable of imparting flexibility of a substrate, an epoxy insulating layer having excellent adhesion to other substrates and plating adhesion; And an insulating resin sheet in which a thermoplastic polyimide layer having a predetermined roughness surface is formed on the surface is sequentially stacked, and thus, a finer circuit can be realized, and high adhesion and excellent moisture absorption and heat resistance characteristics can be obtained.
  • the thickness of the flexible printed circuit board can be significantly reduced, and the manufacturing flexibility can be secured by minimizing the structural bending characteristics as a final product.
  • 1 to 3 are cross-sectional views showing the configuration of an insulating resin sheet according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view showing a manufacturing process of an insulating resin sheet according to an embodiment of the present invention.
  • FIG. 5 is a scanning electron microscope (SEM) photograph of a microcircuit pattern of the insulating resin sheet prepared in Example 1 by applying a semi-additive method.
  • thermoplastic polyimide layer 40 release film
  • a build-up material capable of forming an insulating layer when manufacturing a printed circuit board
  • it is characterized by providing a novel insulating resin sheet exhibiting 'excellent adhesion to the substrate and the plating layer' and 'hygroscopic heat resistance characteristics'.
  • the said insulating resin sheet is a (A) polyimide film; (B) an epoxy insulating layer formed on one side or both sides of the polyimide film; And (C) a thermoplastic polyimide layer formed on the epoxy insulating layer and having a predetermined surface roughness formed on the surface thereof, respectively, sequentially stacked (see FIGS. 1 and 2).
  • the epoxy insulating layer is a resin layer mixed with an optimized dimer acid-modified epoxy resin and a benzoxazine-based resin, and improves the interlayer adhesion strength of the polyimide film and the thermoplastic polyimide layer based on the excellent binding force expressed from the benzoxazine. It is possible to prevent the drilling failure due to the decrease in adhesion during the PCB manufacturing process. In addition, it is possible to exhibit low hygroscopic properties and excellent hygroscopic heat-resistance characteristics expressed from ring-opening polymerization of intramolecular benzoxazine rings.
  • thermoplastic polyimide layer is formed by the electroless copper plating layer formed by the plating process after the plating process due to the anchoring effect of fine roughness formed through the transfer of the mat surface of the copper foil and the intermolecular occurring at the interface. Adhesion strength can be improved more.
  • the thermoplastic polyimide layer is positioned below the pattern layer, the impurities having an impurity such as an additive is low compared to the substrate having the epoxy resin as an insulating layer, and thus the ion migration characteristics by the accelerated test are relatively low.
  • an insulating resin sheet having high adhesion and excellent moisture absorption and heat resistance characteristics can be provided by introducing an epoxy resin insulating layer having high adhesion with polyimide.
  • the insulating resin sheet of the present invention can increase the degree of freedom of product design by applying a flexible polyimide (PI) film.
  • PI polyimide
  • the insulating resin sheet of the present invention comprises a polyimide film 10; An epoxy insulating layer 20 formed on one or both surfaces of the polyimide film; And a thermoplastic polyimide layer 30 formed on the epoxy insulating layer and having a predetermined surface roughness formed thereon, each having a structure in which they are sequentially stacked.
  • the polyimide film 10 not only serves as a base support film that physically supports the insulated resin sheet, but also has a heat resistance and flexibility, thereby increasing the degree of freedom in product design. have.
  • the polyimide film may contain an inorganic filler, if necessary, to adjust the substrate thermal expansion coefficient (CTE).
  • Polyimide (PI) resin is a polymer material having an imide ring, and exhibits excellent heat resistance, ductility, chemical resistance, abrasion resistance and weather resistance based on the chemical stability of the imide ring. Thermal expansion coefficient, low breathability and excellent electrical properties.
  • the polyimide film may have a film to sheet shape having self-supportability.
  • a commercially available polyimide film may be used, or the condensation reaction of a diamine compound and a tetra carboxylic acid compound according to a method known in the art may be followed by coating and drying / curing such a reactant on a substrate. It may be prepared by.
  • the thickness of the polyimide film can be appropriately adjusted in consideration of the handleability of the film, physical rigidity, thermal expansion coefficient, thinning of the substrate, high density wiring, and the like. For example, it may be in the range of 5 to 100 ⁇ m, preferably in the range of 12.5 to 50 ⁇ m, and more preferably in the range of 12.5 to 25 ⁇ m.
  • the surface of the polyimide film may be a surface treatment such as matt treatment, corona treatment.
  • the polyimide film layer is known in the art
  • Conventional inorganic fillers may be included.
  • Non-limiting examples of inorganic fillers that can be used include silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fibers, aluminum borate, barium titanate, strontium titanate, calcium titanate , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica and the like.
  • the amount of the inorganic filler to be used is not particularly limited and may be appropriately adjusted in consideration of the bending property and mechanical properties described above.
  • the polyimide (PI) film which concerns on this invention may contain the laser energy absorptive component in order to further improve the workability of the hole by a laser.
  • the laser energy absorbing component known ones such as carbon powder, metal compound powder, metal powder or black dye can be used. Moreover, these can use any 1 type or 2 or more types together.
  • Examples of the carbon powder include powders of carbon black such as furnace black, channel black, acetylene black, thermal black, anthracene black, graphite powder, or a mixture thereof.
  • Examples of the metal compounds include titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide and zinc oxide, silicon dioxide, aluminum oxide, and rare earth oxide, Cobalt oxides such as cobalt oxide, tin oxides such as tin oxide, tungsten oxides such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, barium sulfate, rare earth sulfides, or mixtures thereof Powder and the like.
  • the metal powder examples include silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, or powders of alloys or mixtures thereof.
  • Carbon powder is preferable from a viewpoint of the conversion efficiency with respect to heat of laser energy, versatility, etc. as a laser energy absorbent component.
  • the upper limit of the average particle diameter of the laser energy absorbent component is preferably in the range of 0.01 ⁇ m to 20 ⁇ m from the viewpoint of efficiently absorbing laser energy.
  • a polyimide (PI) film is mainly described as the base support film, but any other resin is not particularly limited as long as it is a resin film having heat resistance, flexibility, smoothness, and low water absorption.
  • any other resin is not particularly limited as long as it is a resin film having heat resistance, flexibility, smoothness, and low water absorption.
  • PET polyethylene terephthalate
  • polyamideimide film polyamide film
  • polytetrafluoroethylene film polycarbonate film
  • polycarbonate film or a form in which two or more thereof are mixed
  • conventional plastic films known in the art also falls within the scope of the present invention.
  • the epoxy insulating layer 20 is formed on one side or both sides of the polyimide film 10, respectively, and the adhesion between the polyimide film, the thermoplastic polyimide layer, and the copper foil layer is better. It contains the hardened layer formed by hardening
  • thermosetting composition for forming the epoxy insulating layer together with a high equivalent first epoxy resin, a low equivalent second epoxy resin and a curing agent having a narrow molecular weight distribution (Narrow dispersity, ND) as a component thereof has a low molecular weight index (PDI) And an optimized dimer acid-modified epoxy resin and a benzoxazine-based resin.
  • Polydispersity Index is a criterion indicating the extent of the molecular weight distribution of the polymer, and is defined as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
  • PDI polydispersity index
  • the resin having a narrow molecular weight distribution is significantly reduced in the content of relatively high high molecular weight material (eg High Mw species) and low molecular weight material (eg Oligomer), The distribution is generally uniform. Since the ND resin has a relatively high content of a high molecular weight material, as the viscosity is lowered, wetting property of the coating surface is excellent. It has good coating properties and contributes to improved adhesion.
  • relatively high molecular weight material eg High Mw species
  • low molecular weight material eg Oligomer
  • the degree of viscosity decrease of the resin is low, and the filling property is excellent.
  • low viscosity and gel time increase due to narrow dispersity contribute to stable press formability with primer adhesive copper foil (low adhesive strength) PPG (or product). This means improvement in adhesion.
  • the Tg, Td properties are improved by reducing the content of oligomers, which are low molecular weight materials, which contributes to improved heat resistance and reliability. Therefore, in the present invention, by applying the ND resin, it is possible to improve not only the adhesive strength but also the heat resistance and the glass transition temperature (Tg).
  • the adhesive strength may be increased and flame retardancy may be exhibited. That is, in the benzoxazine resin, the benzoxazine ring in the molecule is ring-opened to form a non-halogen primer resin layer together with the epoxy resin.
  • the non-halogen resin layer not only has excellent flame retardancy, but also the low dielectric properties of the benzoxazine resin. Due to its flame retardancy, low hygroscopicity and high glass transition temperature (Tg), it can exhibit excellent mechanical properties.
  • thermosetting resin composition for forming an epoxy insulating layer include: (a) a high equivalent first epoxy resin having an epoxy equivalent (EEW) in the range of 400-1,000 g / eq; (b) low equivalent second epoxy resins having an epoxy equivalent (EEW) in the range of 100-300 g / eq; (c) dimer acid-modified epoxy resins; (d) benzoxazine resins; And (e) two or more curing agents, and at least one of the resins (a) and (b) may include an ND epoxy resin having a polydispersity index (PDI) of 2 or less.
  • PDI polydispersity index
  • it may further include a curing accelerator.
  • this is not particularly limited.
  • the first component of the thermosetting resin composition for forming an epoxy insulating layer according to the present invention is an epoxy resin.
  • the epoxy resin of the present invention is not particularly limited as long as it contains two or more epoxy groups in the molecule.
  • Non-limiting examples of the epoxy resins that can be used include bisphenol A, bisphenol F, cresol novolac, dicyclopentazene, trisphenylmethane, naphthalene, biphenyl type and hydrogenated epoxy resins thereof, alone or in combination. More than one species can be used by mixing. In particular, when using a hydrogenated epoxy resin, it is preferable to use bisphenol A or a biphenyl type epoxy resin.
  • two or more kinds of epoxy resins having different equivalents are mixed as epoxy resins, and at least one or more of epoxy resins having different equivalents has a polydispersity index (PDI) of ND having a narrow molecular weight distribution of 2.0 or less. (narrow dispersity) It is characterized by using a resin.
  • PDI polydispersity index
  • an epoxy equivalent weight (EEW) epoxy resin has a good melt property at low melt viscosity and adhesion, and a high equivalent epoxy resin (EEW) has plasticity in itself. It is possible to further improve molding characteristics such as bending property (bending workability) and punching property of the copper foil or laminate for printed circuit board. Therefore, when an epoxy resin having a degree of polymerization (n) or an equivalent difference is mixed as in the present invention, in addition to the effect due to the use of an ND resin having a narrow molecular weight distribution, high adhesiveness, excellent moisture resistance reliability, moldability, and the like can be exhibited. have.
  • first epoxy resin having an epoxy equivalent of about 400 to 1000 g / eq and a low equivalent second epoxy resin having an epoxy equivalent of about 100 to 300 g / eq as the epoxy resin.
  • first epoxy resin and the second epoxy resin may be used alone, or two or more kinds of resins having the aforementioned equivalent ranges may be used.
  • the weight average molecular weight (Mw) of the first epoxy resin is in the range of 1,000 to 3,000, and the weight average molecular weight (Mw) of the second epoxy resin is preferably in the range of 500 to 2,000.
  • the use ratio of the first epoxy resin and the second epoxy resin may be 50 to 90: 10 to 50 weight ratio, preferably 50 to 70: 30 to 50 range. have.
  • the first epoxy resin, the second epoxy resin, or both thereof may have a polydispersity index (PDI) of 2 or less, preferably 1 to 1.7, and more preferably 1.1 to 1.5.
  • PDI polydispersity index
  • T g glass transition temperature of the epoxy resin
  • it may range from 80 to 250 ° C, or may be from 90 to 200 ° C.
  • the present invention may further include a conventional epoxy resin known in the art, and is not particularly limited thereto.
  • the content of the epoxy resin may be in the range of 20 to 70 parts by weight with respect to 100 parts by weight of the total resin composition, preferably in the range of 30 to 60 parts by weight, more preferably. Preferably from 40 to 60 parts by weight.
  • the content of the epoxy resin falls within the above-mentioned range, the curability, molding processability and adhesion of the resin composition are good.
  • the third component of the thermosetting resin composition for forming an epoxy insulating layer according to the present invention is a dimer acid-modified epoxy resin.
  • the dimer acid-modified epoxy resin forms an adhesive composition by a curing reaction, it is easy to form a cured product given flexibility by structural factors of the dimer acid-modified portion, and by imparting elastomeric properties to the adhesive layer (insulator)
  • the adhesiveness, heat resistance, and moisture resistance of the copper base which is a metal base, and an adhesive bond layer (insulator) can be improved.
  • Non-limiting examples of the dimer acid-modified epoxy resin that can be used are KSR-200 (Kukdo Chemical), SER-200 (Shin-A T & C), etc. These may be used alone or in combination of two or more.
  • examples of the dimer acid-modified epoxy resin include an epoxy resin represented by the following Chemical Formula 1, but are not limited thereto.
  • the dimer acid-modified epoxy resin has a modification rate of about 5 to 30%, cracking and peeling phenomena do not occur during punching processing, and thus heat resistance and moisture resistance may be further improved.
  • the epoxy equivalent and viscosity of the dimer acid-modified epoxy resin are not particularly limited, but when the epoxy equivalent is about 100 to 500 g / eq and the viscosity is about 5,000 to 30,000 cps, the cohesive breakage does not occur, Formability such as bending workability) and punching workability and heat resistance and moisture resistance can be further improved.
  • the content of the dimer acid-modified epoxy resin may be in the range of about 5 to 40 parts by weight based on 100 parts by weight of the mixture of the epoxy resin and the curing agent, preferably 5 to It may range from 30 parts by weight.
  • the content of the dimer acid-modified epoxy resin falls within the above-mentioned range, molding processability, heat resistance, adhesiveness and the like of the resin composition are good.
  • thermosetting resin composition for epoxy insulating layer formation which concerns on this invention is benzoxazine type resin.
  • the benzoxazine resin is a thermosetting resin mainly containing a compound having a benzoxazine ring, and is not particularly limited as long as it is a resin having a benzoxazine ring and cured by the ring-opening reaction of the benzoxazine ring.
  • the benzoxazine resin is a condensate of an oxazine and a benzene ring, and generally can be synthesized by reacting phenols, amines, and formaldehyde.
  • a compound having a single benzoxazine ring (ring) in a molecule, a compound having a benzoxazine structure at both ends, or a polyvalent oxazine compound having a plurality of benzoxazine rings in a molecule can be used.
  • the benzoxazine resin may be ring-opened and cured by heating to provide a cured product having excellent heat resistance and flame resistance. Moreover, it can also react with an epoxy resin and can form hardened
  • benzoxazine having a polyol content of 80% or more.
  • benzoxazine-based resins of various structures can be applied, it is preferable to use BPF-type benzoxazine-based resins because of excellent hygroscopicity and reactivity.
  • the content of the benzoxazine-based resin may be in the range of 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent. It may be a minor range.
  • the content of the benzoxazine resin falls within the above range, the curability, flame retardancy, low hygroscopicity, and adhesion of the resin composition are good.
  • thermosetting resin composition for forming an epoxy insulating layer according to the present invention is a curing agent commonly used in the art.
  • the curing agent may be appropriately selected and used depending on the type of epoxy resin, and is not particularly limited as long as it is usually used as a curing agent for epoxy resins.
  • a curing agent a first curing agent participating in the ring-opening reaction of the benzoxazine resin; And it is preferable to mix with the epoxy resin and the 2nd hardening agent which advances hardening reaction.
  • non-limiting examples of the first curing agent include a phenol novolak curing agent, an imidazole, an amine curing agent, and the like, and the structure thereof is not particularly limited.
  • phenol novolak-based curing agents are preferred because they can further improve heat resistance and adhesion.
  • the second hardener examples include cresol novolac, bisphenol A novolac, naphthalene type, amine hardener, aminotriazine novolac, and the like, and the structure thereof is not particularly limited. These may be used alone or in combination of two or more thereof.
  • At least one of the first and second curing agents preferably has a polydispersity index (PDI) of 2 or less, more preferably 1 to 1.7, still more preferably 1.1 to 1.5.
  • PDI polydispersity index
  • the first hardener or the second hardener may have a PDI of 2 or less, or both of them may use a PDI of 2 or less.
  • the content of the curing agent may be appropriately adjusted according to the content of the epoxy resin.
  • the curing agent and the epoxy resin may be reduced from 20 to 50:50 to 50%. It is preferable to mix and use in 80 weight ratio.
  • it may further include a conventional curing accelerator known in the art.
  • the curing accelerator may be appropriately selected and used depending on the type of the epoxy resin and the curing agent.
  • curing accelerators that can be used include amine-based, phenol-based, and imidazole-based curing accelerators, and more specific examples thereof include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride, and trimellitic anhydride. have.
  • the curing accelerators include imidazole derivative curing accelerators, specifically 1-methylimidazole, 2-methylimidazole, 2-ethyl 4-methyl imidazole, 2-phenylimidazole. , 2-phenyl4-methyl imidazole, cyanoethylation derivatives thereof, carboxylic acid derivatives, hydroxymethyl group derivatives, and the like, but are not limited thereto.
  • These hardening accelerators can be used individually by 1 type, or can also use 2 or more types together.
  • the amount of the curing accelerator may be in the range of about 0.005 to 0.05 parts by weight, preferably 0.01 to 0.04, based on 100 parts by weight of the mixture of the epoxy resin and the curing agent.
  • thermosetting resin composition for forming the epoxy insulating layer of the present invention inorganic fillers, flame retardants, and other thermosetting resins and thermoplastics not generally described above, which are generally known in the art, as long as they do not impair the intrinsic properties of the resin composition.
  • Various polymers such as resins and oligomers thereof, solid rubber particles or other additives such as UV absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents, and the like may be further included.
  • Examples include flame retardants such as organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides; Organic fillers such as silicone powder, nylon powder, and fluororesin powder, and thickeners such as orbene and benton; Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, and silane coupling agents; Phthalocyanine, carbon black, etc. can be mentioned a coloring agent.
  • flame retardants such as organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides
  • Organic fillers such as silicone powder, nylon powder, and fluororesin powder, and thickeners such as orbene and benton
  • Polymeric antifoaming agents or leveling agents such as silicone-based and fluorine-based resins
  • Adhesion imparting agents such as imidazole
  • thermoplastic resin can be mix
  • thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimides, polyamideimide, polyethersulfone, polysulfone and the like. Any one of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.
  • the epoxy insulating layer 20 according to the present invention is formed by directly coating a thermosetting resin composition for forming an epoxy insulating layer on one or both surfaces of the polyimide film 10.
  • the thickness of the epoxy insulating layer 20 formed by including the above-described components is not particularly limited, and may be, for example, in the range of 1 to 50 ⁇ m, and preferably in the range of 10 to 30 ⁇ m.
  • the epoxy insulating layer 20 may exhibit excellent adhesion between the polyimide film 10 and the thermoplastic polyimide layer 30 by chemical bonding of a benzoxazine ring and a dangling bond on the polyimide surface. Can be.
  • the dimer acid-modified epoxy resin which is a component of the resin composition can also increase the peel strength by imparting elasticity of the polyimide film 10 and the thermoplastic polyimide layer 30 from the elastomeric properties according to the molecular structure.
  • the adhesion with the polyimide film 10 may preferably range from 0.7 to 2.0 kgf / cm 2 .
  • thermoplastic polyimide layer 30 is formed on the surface of the epoxy insulating layer 20, or on the upper and lower surfaces thereof, and a predetermined roughness surface is formed on the surface thereof. Adhesion with is improved.
  • thermoplastic polyimide (TPI) layer is cured after liquid coating a resin composition for forming a thermoplastic polyimide layer comprising at least one resin selected from the group consisting of polyimide, polyamide, polyamideimide, and polyamic acid resin. It includes that formed. Or commercially available soluble polyimide (soluble PI).
  • the composition for forming a thermoplastic polyimide layer may be composed of a polyimide (PI) -based first resin and a surfactant, and may further include a second resin such as an epoxy resin as necessary.
  • PI polyimide
  • the polyimide (PI) is generally synthesized by condensation polymerization of an aromatic dianhydride and an aromatic diamine (or aromatic diisocyanate), and the polyimide is preferably a thermosetting polyimide.
  • Non-limiting examples of the polyimide resin that can be used include polyimide, polyamideimide, composite resins thereof and the like.
  • the polyimide-based resin may be prepared by imidization of a polyamic acid varnish obtained through imidation reaction of a typical dianhydride and diamine known in the art.
  • the content of the polyimide-based resin may range from 70 to 100 parts by weight with respect to 100 parts by weight of the total resin composition, preferably 80 to 100 parts by weight. have.
  • the content of the polyimide resin falls within the above-mentioned range, the curability, molding processability, and adhesion of the resin composition are good.
  • the surfactant can be used without limitation to conventional surfactant components known in the art.
  • the said surfactant is a component which has the effect of adjusting the surface tension of the said resin composition varnish for thermoplastic polyimide layer formation, and improving coating property, coating property, uniformity, etc. with respect to copper foil which is a coating base material.
  • Non-limiting examples of the surfactants that can be used include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants or mixtures of one or more thereof.
  • the content of the surfactant may be in the range of 0.001 to 0.1 parts by weight based on 100 parts by weight of the total resin composition, and preferably in the range of 0.001 to 0.05 parts by weight.
  • the content of the surfactant falls within the above-mentioned range, the coating property, the coatability, and the uniformity of the resin composition on the substrate are good.
  • the resin composition for thermoplastic polyimide layer formation which concerns on this invention can contain 2nd resin, such as an epoxy resin, as needed.
  • the epoxy resin may be used without limitation conventional epoxy resin known in the art, and may be the same as or different from the components used in the composition for forming the epoxy insulating layer described above.
  • the content of the epoxy resin may be in the range of 0 to 30 parts by weight based on 100 parts by weight of the total resin composition, and preferably in the range of 0 to 20 parts by weight.
  • the content of the epoxy resin falls within the above-mentioned range, the curability, molding processability and adhesion of the resin composition are good.
  • the resin composition for forming a thermoplastic polyimide layer of the present invention may further include an additive such as an inorganic filler.
  • an additive such as an inorganic filler.
  • the inorganic filler include silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, or titanate, but are not limited thereto.
  • thermoplastic resin can be mix
  • thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyethersulfones, polysulfones, and the like. Any one of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.
  • thermoplastic polyimide layer 30 the above-described composition for forming a thermoplastic polyimide layer is directly coated on the surface of the epoxy insulating layer 20 and dried, and then the surface roughness surface of the copper foil is transferred to a predetermined surface roughness surface. It can be prepared by forming a.
  • the surface roughness Ra of the thermoplastic polyimide layer 30 may range from 0.2 ⁇ m to 3.0 ⁇ m.
  • the method of transferring is not particularly limited, and for example, may be achieved by laminating a copper foil and a thermoplastic polyimide layer having a predetermined roughness surface on a surface thereof and then pressing the same.
  • the thickness of the thermoplastic polyimide layer 30 may be in a range of 1 to 50 ⁇ m, preferably 10 to 30 ⁇ m. It can be a range.
  • the sum of the thicknesses of the epoxy insulating layer 20 and the thermoplastic polyimide layer 30 may be in the range of 1 to 30% of the total thickness, and preferably in the range of 1 to 20%. have.
  • the insulating resin sheet according to the present invention may further include a support layer 40 on the thermoplastic polyimide layer 30.
  • a plastic film may be used as the support, and a metal foil such as a release paper, a copper foil, or an aluminum foil may also be used as the support.
  • a metal foil such as a release paper, a copper foil, or an aluminum foil
  • the plastic film that can be used include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; Polycarbonate, acrylic resin, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, polyimide and the like.
  • a release layer treated with a release agent between the polyimide layer 30 and the support layer 40 As the release agent used in the release layer, if the thermoplastic polyimide layer is completely peelable from the support, it is not particularly limited to its components, and conventional release agent components known in the art may be used. Non-limiting examples thereof include an epoxy-based release agent, a release agent made of a fluororesin, a silicone release agent, an alkyd resin release agent, a water-soluble polymer, and the like.
  • the plastic film may be matt, corona treated, or may form a release layer on the treated surface.
  • the thickness of the support layer 40 is not particularly limited, but may be in the range of 10 to 150 ⁇ m, and preferably in the range of 25 to 50 ⁇ m.
  • the total thickness of the insulating resin sheet may be in the range of 7 to 200 ⁇ m, preferably in the range of 10 to 150 ⁇ m.
  • the insulating resin sheet for forming a flexible printed circuit board according to the present invention may be manufactured by the following method. However, this is not particularly limited.
  • FIG. 4 is a cross-sectional view showing a manufacturing process of an insulating resin sheet according to an embodiment of the present invention.
  • thermosetting resin composition for forming the epoxy insulating layer is coated and dried to dry the epoxy insulating layer Forming; (ii) coating a composition for forming a thermoplastic polyimide layer on the epoxy insulating layer and then drying to form a thermoplastic polyimide layer; And (iii) laminating the polyimide film and the copper foil having a predetermined surface roughness, wherein the thermoplastic polyimide layer of the polyimide film and the surface roughness surface of the copper foil are disposed to be in contact with each other, and then heated and pressurized onto the surface of the thermoplastic polyimide layer. It can be configured to include a step characterized by transferring the surface roughness surface of the copper foil.
  • the resin composition for forming the epoxy insulating layer when applied on the polyimide film base material, for example, a roll coater, bar coater, coater coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater It can be carried out by applying a thermosetting resin composition on a substrate with a transfer roll coater, gravure coater, spray coater and the like, and drying for 1 to 30 minutes at a temperature of 50 to 130 °C.
  • the above-described coating method can be used in the same manner.
  • organic solvents examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate.
  • acetic acid esters such as carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent 1 type or in combination of 2 or more types.
  • the step (iii) may be carried out by laminating the thermoplastic polyimide layer of the polyimide film and the surface roughness surface of the copper foil so as to contact each other, and then heating and pressing. At this time, it is preferable to completely cure the thermoplastic polyimide resin composition through a roll lamination or a press process.
  • the conditions of the roll lamination, press process, etc. are not particularly limited, and may be appropriately adjusted under conventional conditions known in the art.
  • FCCL Flexible Copper Clad Laminate
  • This invention provides the flexible copper foil laminated board using the above-mentioned insulated resin sheet.
  • the flexible copper foil laminate refers to a laminate in which a polyimide film and a copper foil are bonded as a material of a flexible printed circuit board (FPCB).
  • FPCB flexible printed circuit board
  • the flexible copper foil laminate comprises an insulating resin sheet; And copper foil layers formed on upper and lower surfaces of the thermoplastic polyimide layer of the insulating resin sheet, respectively.
  • the copper foil layer may use any conventional copper foil known in the art without limitation, and includes all copper foils manufactured by a rolling method and an electrolytic method.
  • it may be formed by an electroplating layer, an electroless plating layer, or a sputtering method.
  • the copper foil layer may have a predetermined surface roughness Ra, in which case the surface roughness is not particularly limited, and may be, for example, in a range of 0.2 ⁇ m to 3.0 ⁇ m.
  • the thickness of the copper foil layer is not particularly limited, and may be less than 3 ⁇ m in consideration of the thickness and mechanical properties of the final product.
  • a predetermined pattern may already be formed in the said copper foil layer.
  • the present invention provides a printed circuit board, preferably a flexible printed circuit board (FPCB), manufactured using an insulating sheet.
  • a printed circuit board preferably a flexible printed circuit board (FPCB), manufactured using an insulating sheet.
  • FPCB flexible printed circuit board
  • the printed circuit board refers to a printed circuit board laminated in a single layer or two or three or more layers by a plating through hole method, a buildup method, or the like.
  • the flexible printed circuit board of the present invention is easy to form the roughness and the plating after the semi-additive method to implement a fine circuit pattern, as well as to minimize the side of the pattern generated during the electroplating Surface roughness can form a dense and regular shape can have excellent plating adhesion.
  • the printed circuit board is an insulating resin sheet; Copper foil plating layers respectively formed on the upper and lower surfaces of the thermoplastic polyimide layer of the said insulated resin sheet, and have a predetermined pattern; And a plurality of through holes provided to penetrate the insulating resin sheet and plated to electrically connect patterns of copper foil plating layers respectively formed on upper and lower surfaces thereof.
  • the line / space (L / S) of the circuit pattern may range from 2 ⁇ m / 2 ⁇ m to 30 ⁇ m / 30 ⁇ m, but is not particularly limited thereto.
  • the printed circuit board according to the present invention can be manufactured by conventional methods known in the art, for example, semi-additive, except for using the above-described insulating resin sheet.
  • the manufacturing method For a preferred embodiment of the manufacturing method, (I) forming at least one hole in the above-mentioned insulating resin sheet; (II) desmearing the surface of the film and the inside of the hole to form roughness; (III) forming an electroless plating layer on the rough surface and the inner surface of the hole of the film; (IV) forming a pattern using a photoresist on the formed electroless plating layer; (V) forming a circuit layer by electroplating on the pattern; And (VI) exfoliating the photoresist and removing the exposed electroless plating layer.
  • One or more holes are formed in the insulating resin sheet.
  • a laser is irradiated to the said insulated resin sheet, and a hole is formed.
  • the laser may use an excimer laser, a UV laser, a carbon dioxide gas (CO 2 ).
  • the insulating resin sheet of the present invention is already formed on the outermost rough surface, not only does not require a special chemical etching process, but even if the chemical etching process, even better than the polyimide (PI) chemical resistance
  • PI polyimide
  • the thermoplastic polyimide layer (TPI) is present at the outside, a decrease in plating adhesion due to chemical etching may be minimized.
  • the desmear process removes resin residues (smear) after laser irradiation by oxidizing agents such as permanganate, dichromate, etc., and this step removes the surface of the insulating resin sheet and the inner surface of the hole by laser processing.
  • the roughness surface which has a suitable roughness (roughness) is formed by processing.
  • the surface of the smooth insulated resin sheet can be harmonized simultaneously, and the adhesiveness of the electrically conductive wiring circuit formed by the metal plating which follows is improved.
  • an etching process may be further performed to maintain a horizontal roughness surface having an appropriate roughness on the insulating resin sheet after the desmear process.
  • the surface of the insulated resin sheet after a desmear process has preferable roughness for forming a fine circuit pattern.
  • the surface roughness range of the insulating resin sheet after the desmear process may be in the range of 50 nm to 1,000 nm, preferably in the range of 100 nm to 500 nm.
  • An electroless plating layer is formed on the roughness surface and the hole inner surface of the insulating resin sheet.
  • Electroless plating is performed on the roughness surface and the inner surface of the hole to form a relatively thin plating layer.
  • Such an electroless plating layer is to secure the adhesive strength to the thermoplastic polyimide layer in advance in order to raise the fine circuit pattern layer to be formed thereon.
  • the adhesion between the circuit electrode to be formed and the substrate has a close relationship, and an electroless plating layer is formed between the substrate and the circuit electrode.
  • the electroless plating layer is formed using the surface-coated catalyst as an active point, ultimately there is no adhesion with the substrate. Therefore, when the roughness of the substrate surface is large, the adhesion between them is maintained well by the anchor effect, but when the roughness is not present on the substrate surface, the adhesiveness tends to be lowered. Therefore, it is preferable to obtain a good circuit shape by adjusting it to have a surface roughness of about 0.1 times or less of the formed circuit width.
  • the said electroless plating layer used as the seed layer of an electrolytic plating layer is generally 0.1-5 micrometers.
  • a pattern is formed on the formed electroless plating layer using photoresist.
  • a fine circuit pattern is formed by coating a photoresist as a lithography process and forming an opening for forming an outer layer pattern.
  • the photoresist may be a dry film or the like.
  • a circuit layer by electroplating is formed on the pattern.
  • a conductor layer for forming the fine circuit pattern in the opening of the photoresist layer is formed by electroplating.
  • the electrolytic plating layer forms a new circuit layer connected to the plated copper foil layer by the hole.
  • the thickness of the electroplating layer is preferably in the range of about 1 ⁇ m to 100 ⁇ m.
  • the line / space of the circuit pattern formed in this step may be less than 30 ⁇ m / 30 ⁇ m, preferably in the range of 2 ⁇ m / 2 ⁇ m ⁇ 30 ⁇ m / 30 ⁇ m, more preferably 2 ⁇ m / 2 ⁇ m ⁇ 20 ⁇ m / 20 May be in the ⁇ m range.
  • the line space L / S of the circuit pattern formed in the present invention is 10 ⁇ m / 10 ⁇ m (see FIG. 5).
  • circuit pattern is completed by removing the unnecessary photoresist layer and removing the exposed electroless plating layer.
  • the manufacturing is completed by further performing a manufacturing process of a conventional printed circuit board known in the art, such as an electronic device mounting process.
  • the above-described method of manufacturing a printed circuit board is not to be manufactured by sequentially performing the above-described steps, but may be performed by modifying or selectively mixing the steps of each process according to design specifications.
  • the epoxy resin composition was prepared by mixing a first epoxy resin, a second epoxy resin, a first curing agent, a second curing agent, a dimer acid-modified epoxy resin, a benzoxazine-based resin, a curing accelerator, and the like.
  • the amount of each unit used is parts by weight, where "parts by weight” is based on 100 parts by weight of a mixture of a high equivalent epoxy resin, a low equivalent epoxy resin, and a curing agent.
  • thermoplastic polyimide composition which is a soluble polyimide of soluble DIC
  • the coating layer was formed to a thickness of 4 ⁇ m, and then dried in a 150 ° C. dryer for about 5 to 10 minutes. Thereafter, after lamination using a copper foil having a roughness surface formed on the manufactured thermoplastic polyimide layer, the insulating resin sheet was manufactured by pressing.
  • a flexible printed circuit board was fabricated by performing the hole processing, the desmear treatment, the electroless plating layer formation, and the circuit formation process, respectively, according to the semi additive process using the insulating resin sheet prepared above. It was. The thickness of the plating layer formed at this time was 12 ⁇ m.
  • the insulating resin sheet and the flexible printed circuit board were manufactured in the same manner as in the above embodiment.
  • the amount of each composition is used in parts by weight.
  • a printed circuit board was manufactured in the same manner as in the above example, except that general polyimide (PI) for general FCCL was used.
  • PI general polyimide
  • PI adhesion 1-5 ⁇ m epoxy resin was coated on the untreated polyimide film using a slot die coater (* thin film coatable micro coater). After drying for 2 minutes at 150 °C by B-stage, 5 ⁇ m coated thermosetting polyimide, lamination at 200 °C with Matt surface of 12 ⁇ m (1 / 3Oz) copper foil, evaluation specification of IPC-TM-650 2.4.8 The circuit pattern was formed in the laminated body for printed circuit boards by this. Thereafter, the formed circuit patterns were pulled in the 90 ° direction to measure and evaluate the time points at which the circuit patterns (copper layers) were peeled off.
  • Hygroscopic heat resistance After leaving for 24 hours in a constant temperature and humidity chamber at 85 ° C., 85%, primer resin layer by floating the laminate for printed circuit board at Solder 288 ° C. according to IPC TM-650 2. 4. 13 evaluation standard. The time until the separation phenomenon between the copper foil and the copper foil was measured and evaluated.
  • HAST It was evaluated according to the JEDEC JESD22-A110 evaluation standard.
  • ND hardener 1 phenol novolac hardener (KOLON KPH-F2003, PDI: 1.40 / EEW 106.8)
  • Hardener 2 ATN (aminotrazine novolac) hardener
  • the insulating resin sheet of the present invention showed excellent properties in terms of adhesion to the polyimide film, water absorption, heat absorption and HAST (Highly Accelerated Stress Test) (see Table 1).
  • Ra value was measured using a non-contact 3D Optical Profiler (Bruker Contour GT).
  • the Ra value is an average value of the heights calculated over the entire measurement area. More specifically, the absolute value of the height that changes in the measurement area is measured and arithmetic averaged from an average line surface. It is the value measured by obtaining roughness.
  • Rate of change To quantify the change in plating adhesion measured after high temperature thermal shock, the value obtained by subtracting the changed adhesive force through the high temperature thermal shock to the initial adhesive strength and then dividing by the percentage.
  • the insulating resin sheet of the present invention exhibited excellent properties in terms of surface roughness, adhesion, plating adhesion, high temperature adhesion, and rate of change (see Table 2). Therefore, it is possible to manufacture a reliable build-up printed circuit board in the future, and it is judged that it will be usefully used as a constituent material of a small and lightweight new semiconductor package.

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Abstract

La présente invention concerne une feuille de résine isolante pour la formation d'une carte de circuit imprimé souple (FPCB), un procédé de fabrication correspondant, et une carte de circuit imprimé souple comprenant ladite feuille de résine isolante, la feuille de résine isolante comprenant : un film polyimide ; une couche isolante époxy formée sur une ou sur les deux surfaces du film polyimide ; et une couche polyimide thermoplastique, laquelle est formée sur la couche isolante époxy, et possède une rugosité de surface prédéterminée formée à sa surface. La présente invention peut fournir une feuille de résine isolante permettant de réaliser simultanément une bonne fixation par adhésion, une résistance à la chaleur, et un motif de microcircuit, et une carte de circuit imprimé assemblée l'utilisant.
PCT/KR2014/012815 2013-12-27 2014-12-24 Feuille de résine isolante pour la formation d'une carte de circuit imprimé souple, son procédé de fabrication et carte de circuit imprimé la comprenant WO2015099451A1 (fr)

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KR1020130166193A KR101571086B1 (ko) 2013-12-27 2013-12-27 연성 인쇄회로기판 형성용 절연 수지 시트 및 이의 제조방법, 이를 포함하는 인쇄회로기판

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