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WO2014092428A1 - Carte de circuits imprimés multicouche, et procédé de fabrication correspondant - Google Patents

Carte de circuits imprimés multicouche, et procédé de fabrication correspondant Download PDF

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Publication number
WO2014092428A1
WO2014092428A1 PCT/KR2013/011395 KR2013011395W WO2014092428A1 WO 2014092428 A1 WO2014092428 A1 WO 2014092428A1 KR 2013011395 W KR2013011395 W KR 2013011395W WO 2014092428 A1 WO2014092428 A1 WO 2014092428A1
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WO
WIPO (PCT)
Prior art keywords
layer
resin
insulating resin
insulating
resin sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2013/011395
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English (en)
Korean (ko)
Inventor
박광석
정수임
김형규
김인욱
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Doosan Corp
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Doosan Corp
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Filing date
Publication date
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Publication of WO2014092428A1 publication Critical patent/WO2014092428A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer

Definitions

  • the present invention provides an insulation resin sheet for forming an insulation layer of a build-up printed circuit board that can reduce the overall thickness of the laminate, provide flexibility of the substrate, improve freedom of product design, and implement a high-density microcircuit pattern.
  • a multilayer printed circuit board including the insulating layer and a method for manufacturing the same.
  • a build-up board is used as a package board for semiconductors, which insulates the resin by a build-up method and forms a circuit by a semi-additive method.
  • the semi-additive method is one of methods of forming a circuit of a PCB substrate, and a subtractive method of forming a circuit pattern through etching and plating only a pattern portion to form a circuit
  • the wiring formation method combining the additive method has an advantage that a finer pattern can be formed than the subtractive method.
  • the conventional microcircuit build-up printed circuit board mainly uses prepreg as an interlayer insulating material.
  • prepreg is used as an interlayer insulating material, roughness formation of the insulating layer through the desmear process is difficult. It is impossible to form a fine pattern using a semi-additive method.
  • prepreg may add a large amount of inorganic filler to lower the coefficient of thermal expansion of the substrate, but such a large amount of inorganic filler may cause cracks, bends or wrinkles during processing of wiring circuit formation of a printed circuit board.
  • inorganic filler may cause cracks, bends or wrinkles during processing of wiring circuit formation of a printed circuit board.
  • the present invention has been made in order to solve the above-described problems, the insulating resin sheet comprising a flexible polyimide film and an insulating resin layer capable of a fine circuit pattern laminated with an inner layer wiring board and heated and pressed to form a laminate after desmear
  • the roughness is formed in the circuit forming portion to improve the adhesive strength between the roughness surface of the insulating layer and the plating layer by the plating process, and at the same time to realize the reduction of the overall lamination thickness and implementation of the fine circuit pattern to realize the present invention
  • an object of the present invention is to provide an insulated resin sheet having a novel laminated structure in which roughness can be formed by desmear treatment while providing flexibility to a substrate and increasing the degree of freedom in designing a product.
  • the present invention includes an insulating layer formed by using the insulating resin sheet, thereby reducing the defects in the circuit formation process, the multilayer printed circuit that can simultaneously exhibit the reduction of the thickness of the laminate, the adhesion strength between the layers, heat resistance and long-term reliability. Another object is to provide a substrate and a method of manufacturing the same.
  • the present invention is a polyimide film; An adhesive layer formed on one surface of the polyimide film; And an insulated resin layer formed on the other side of the polyimide film, the insulator resin layer capable of roughness formation by a desmear process.
  • the insulating resin layer (a) polyphenylene ether is 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- Polyphenylene ether modified resin obtained by redistribution in the presence of (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide (HCA-HQ); (b) epoxy resins; (c) curing agents; And (d) curing the thermosetting resin composition comprising at least one modified epoxy resin selected from the group consisting of dimer acid-modified epoxy resins, urethane-modified epoxy resins, and carboxyl-terminated butadiene acrylonitrile (CTBN).
  • CTBN carboxyl-terminated butadiene acrylonitrile
  • thermosetting resin composition includes a polyphenylene ether modified resin (a) which is redistributed to polyphenylene ether in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF) (e) It is preferable to further include.
  • the polyphenylene ether modified resin (a) is a redistribution reaction of a high molecular weight polyphenylene ether resin having a number average molecular weight in the range of 10,000 to 30,000 and modified to a low molecular weight having a number average molecular weight in the range of 1,000 to 15,000. It is preferred that the redistribution reaction is carried out in the presence of an initiator, a catalyst or a radical initiator and a catalyst.
  • the epoxy resin (b) is preferably a mixture of two or more epoxy resins having different epoxy equivalents
  • the modified epoxy resin (d) has an epoxy equivalent in the range of 100 ⁇ 500 g / eq
  • the viscosity is 5,000 ⁇ 30,000 cps It is preferable that it is a range.
  • the resin composition for forming an insulated resin layer may include (a) 10 to 60 parts by weight of a polyphenylene ether modified resin; (b) 10 to 40 parts by weight of the epoxy resin; (c) 10 to 40 parts by weight of the curing agent; And (d) 5 to 40 parts by weight of a modified epoxy resin, wherein the polyphenylene ether modified resin (a) is polyphenylene ether in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF) When redistributed under, it is preferable to further include a flame retardant (e) in the range of 5 to 40 parts by weight relative to 10 to 60 parts by weight of the polyphenylene ether modified resin.
  • a flame retardant e
  • the polyimide film may be applied to a product that is used for general purposes, the adhesive layer is applied to the epoxy-based adhesive having a flexibility having adhesion to the inner layer circuit board.
  • the thickness of the polyimide film is in the range of 5 ⁇ m to 100 ⁇ m
  • the thickness of the adhesive layer is in the range of 1 ⁇ m to 50 ⁇ m
  • the thickness of the insulating resin layer is preferably in the range of 1 ⁇ m to 50 ⁇ m.
  • a support layer may be further included on the insulating resin layer, and may further include a release layer between the insulating resin layer and the support layer.
  • this invention provides the multilayer printed circuit board with which the insulating layer was formed by the above-mentioned insulating resin sheet.
  • this invention provides the manufacturing method of a multilayer printed circuit board using the above-mentioned insulating resin sheet.
  • the manufacturing method includes (i) laminating one or more of the above-described insulating resin sheets on one or both surfaces of the inner layer wiring board, and arranging the adhesive layer of the insulating resin sheet to contact the metal surface of the wiring board.
  • the polyimide film that can impart the flexibility of the substrate and the insulating resin sheet in which the roughness can be formed in the desmear process are used are sequentially laminated, an insulating circuit having a fine circuit is formed during laser processing. Significantly reduces the incidence of micro-crack in the layers, enabling more precise circuit implementation.
  • the thickness of the printed circuit board can be significantly reduced, and the manufacturing ease can be secured by minimizing the structural bending characteristics as a final product.
  • FIG. 1 is a cross-sectional view showing the configuration of an insulating resin sheet according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view illustrating a manufacturing process of a multilayer printed circuit board according to an exemplary embodiment of the present invention.
  • the present invention is an insulating resin sheet capable of forming an insulating layer when manufacturing a printed circuit board, which can simultaneously reduce the overall thickness of the laminate, give flexibility of the substrate and improve design freedom, and can implement a high-density microcircuit pattern at the same time. It is characterized by providing a novel insulating resin sheet.
  • the insulating resin sheet may comprise (i) a polyimide film; And (ii) an adhesive layer formed on one surface of the polyimide film. And (iii) formed on the other side of the polyimide film, in which an insulating resin layer capable of roughness formation by a desmear process is laminated (see FIG. 1).
  • the insulating resin layer is a resin layer that does not contain an inorganic filler or contains a very small amount, micro-crack by the high content inorganic filler included in the insulating layer in the laser processing step of the printed circuit board manufacturing process. By significantly reducing the incidence rate, more accurate circuit implementation is possible.
  • the soluble material capable of forming roughness by the desmear process was included, the adhesive strength between the roughness surface of the insulating layer and the plating layer formed by the subsequent plating process may be improved.
  • 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
  • an insulated resin layer is formed by hardening a thermosetting resin composition.
  • thermosetting resin composition (a) polyphenylene ether is 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl)- Polyphenylene ether modified resins obtained by redistribution in the presence of 10-phosphaphenanthrene 10-oxide (HCA-HQ); (b) epoxy resins; (c) curing agents; (d) dimeric acids may be composed of one or more modified epoxy resins selected from the group consisting of modified epoxy resins and urethane modified epoxy resins.
  • thermosetting resin composition uses a polyphenylene ether modified resin (a) redistributed to polyphenylene ether in the presence of 9,9-bis (hydroxyaryl) fluorene (BCF), flame retardant (e) It may be configured to include more.
  • BCF 9,9-bis (hydroxyaryl) fluorene
  • the 1st component which comprises the thermosetting resin composition for insulating resin layer formation which concerns on this invention is polyphenylene ether modified resin (a).
  • the increase of the hydrophobic group may enhance the hygroscopic properties and the crosslinking properties may be enhanced to enhance thermal and chemical resistance properties.
  • low dielectric and low loss substrates can be realized through improved dielectric properties.
  • PPE polyphenylene ether modified resin
  • BCF BCF
  • HCA-HQ surface roughness
  • polyphenylene ether (PPE) modified resin containing it has its own flame retardant properties. As a result, it is possible to develop a fine circuit pattern material having excellent flame retardant properties without adding a flame retardant material.
  • the insulating resin sheet and the printed circuit board manufactured using the resin composition of the present invention have the advantage of improving the physical properties such as formability, processability, dielectric properties, heat resistance, adhesive strength.
  • the high molecular weight polyphenylene ether can be used for the polyphenylene ether used as the object of modification, and the number average molecular weight (Mn) can use the thing of 10,000-30,000 as an example.
  • polyphenylene ether is a main skeleton, it will not specifically limit.
  • the molecular weight of the polyphenylene ether modified resin modified by low molecular weight by redistributing the high molecular weight polyphenylene ether resin is not particularly limited, the number average molecular weight (Mn) may be in the range of 1,000 to 15,000.
  • the 9,9-bis (hydroxyaryl) fluorene (BCF) may be at least one compound selected from the group consisting of a compound of Formula 1 to a compound of Formula 3.
  • R One To R 3 are each independently C 1 ⁇ C 6 Alkyl group; p1 is an integer of 1-5, q1 is an integer of 0-4, p1 + q1 is an integer of 5 or less; k1 and k2 are each independently an integer of 0 to 4;
  • R 4 To R 6 are each independently a C 1 ⁇ C 6 Alkyl group; p2 is an integer of 1-4, q2 is an integer of 0-3, p2 + q2 is an integer of 4 or less; k3 and k4 are each independently an integer of 0-4;
  • R 7 To R 10 are each independently C 1 ⁇ C 6 Alkyl group; p3 is an integer of 1 to 3, p4 is an integer of 0 to 4, q3 and q4 are each independently an integer of 0 to 2, p3 + q3 is an integer of 3 or less, and p4 + q4 is an integer of 4 or less Is; k5 and k6 are the integers of 0-4 each independently.
  • 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide is in the group consisting of a compound of formula 4 and a compound of formula 5 It may be one or more compounds selected.
  • R 11 To R 13 are each independently C 1 ⁇ C 6 Alkyl group; p5 is 2 and q5 is an integer of 0-3; k7 and k8 are each independently an integer of 0-4;
  • R 14 To R 17 are each independently a C 1 ⁇ C 6 Alkyl group; p6 and p7 are each independently an integer of 0 to 2, p6 + p7 is 2, p6 + q6 is an integer of 3 or less, and p7 + q7 is an integer of 4 or less; k9 and k10 are the integers of 0-4 each independently.
  • the 9,9-bis (hydroxyaryl) fluorene (BCF) or 9,10-dihydro-9-oxa-10- (dihydroxyaryl) -10-phosphaphenanthrene 10-oxide (HCA-HQ) may proceed in the presence of a radical initiator and / or a catalyst.
  • radical initiator and catalyst may be used conventionally known in the art.
  • radical initiators include t-butylperoxy isopropylmonocarbonate, t-butylperoxy 2-ethylhexyl carbonate, benzoyl peroxide and acetyl Acetyl peroxide, di-t-butyl peroxide, t-butyl peroxylaurate, t-butylperoxybenzoate, It is not limited to this.
  • the radical initiator may be used 0.1 to 5 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether.
  • Such catalysts include cobalt naphthanate.
  • the catalyst may be used in an amount of 0.001 to 0.5 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether.
  • the method for synthesizing the modified polyphenylene ether modified resin by redistributing the polyphenylene ether is not particularly limited and conventional methods known in the art may be applied.
  • BCF 9,9-bis (hydroxyaryl) fluorene
  • HCA-HQ -10-phosphaphenanthrene 10-oxide
  • the radical initiator can be mixed and heated to obtain a modified polyphenylene ether modified resin.
  • the solvent may be a hydrocarbon solvent such as benzene or toluene, but is not particularly limited thereto.
  • the reaction temperature and the reaction time may be appropriately adjusted according to the number average molecular weight of the desired polyphenylene ether resin, non-limiting examples thereof may be reacted for about 60 minutes to 200 °C, 10 minutes to 10 hours.
  • the content of the polyphenylene ether modified resin (a) may be in the range of 10 to 60 parts by weight relative to 100 parts by weight of the total resin composition, preferably 20 to 40 It can be a range.
  • the content of the polyphenylene ether modified resin falls within the above-mentioned range, the curability, molding processability and adhesive strength of the resin composition are good.
  • the 2nd component which comprises the thermosetting resin composition for insulating resin layer formation which concerns on this invention is an epoxy resin (b).
  • the epoxy resin may be used without limitation to conventional epoxy resins known in the art, it is preferred that two or more epoxy groups are present in one molecule.
  • Non-limiting examples of the epoxy resins that can be used include bisphenol A / F / S resins, novolak type epoxy resins, alkylphenol novolak type epoxy, biphenyl type, aralkyl type and naphthol ( Naphthol) type, dicyclopentadiene type, or a mixed form thereof.
  • More specific examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene epoxy resins, biphenyl type epoxy resins, tetramethyl biphenyl type epoxy resins, and phenol novolacs.
  • the above-mentioned epoxy resins may be used alone or in combination of two or more thereof.
  • the first epoxy resin having an epoxy equivalent weight of 400 to 1,000 g / eq; And an epoxy equivalent of 100 to 300 g / eq of the second epoxy resin in a 50 to 90:10 to 50 weight ratio.
  • YD-011 epoxy equivalent: 500 g / eq
  • YD-128 epoxy equivalent: 190 g / eq
  • the content of the epoxy resin may be in the range of 10 to 40 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether modified resin, preferably 15 to 30 parts by weight. It may be a minor range. When 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 3rd component which comprises the thermosetting resin composition for insulating resin layer formation which concerns on this invention is a hardening
  • the curing agent may be used without limitation to conventional curing agents known in the art, may be appropriately selected according to the type of epoxy resin to be used.
  • Non-limiting examples of hardeners that can be used include phenolic, anhydride, dicyanamide, and hardeners, of which phenolic hardeners are preferred because they can further improve heat resistance and adhesion.
  • Non-limiting examples of the phenol-based curing agent include phenol novolak, cresol novolak, bisphenol A novolak, naphthalene type, and the like, these may be used alone or in combination of two or more.
  • the content of the curing agent may be appropriately adjusted according to the content of the epoxy resin.
  • the amount of the curing agent may be in the range of 10 to 40 parts by weight based on 10 to 60 parts by weight of the polyphenylene ether modified resin, preferably 10 to 30 parts by weight. It can be a range.
  • curing agent corresponds to the range mentioned above, curability, strength, heat resistance, and fluidity of a resin composition are favorable.
  • the mixing ratio of the epoxy resin and the curing agent may be a ratio in which the phenolic hydroxyl group equivalent of the curing agent is in the range of 0.4 to 2.0 with respect to the epoxy equivalent of epoxy resin 1, preferably in the range of 0.5 to 1.0 It may be a ratio.
  • the 4th component which comprises the thermosetting resin composition for insulating resin layer formation which concerns on this invention is a modified epoxy resin (d).
  • Non-limiting examples of modified epoxy resins that can be used include dimer acid-modified epoxy resins, urethane-modified epoxy resins, carboxyl-terminated butadiene acrylonitrile (CTBN), and these may be used alone or in combination of two or more thereof. can do.
  • CBN carboxyl-terminated butadiene acrylonitrile
  • Dimeric acid-modified epoxy resins tend to form cured products that are flexible due to structural factors of the dimer acid-modified portion when forming an insulating layer by a curing reaction.
  • the plating adhesion, heat resistance, and moisture resistance can be improved.
  • Such a dimer acid-modified epoxy resin is preferable because the adhesion property is excellent when the modification rate is about 5 to 30% and heat resistance and moisture resistance are further improved.
  • Examples of the dimer acid-modified epoxy resin that can be used include KSR-200 (Kukdo Chemical).
  • 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 plating adhesion, heat resistance and moisture resistance properties can be further improved. desirable.
  • Urethane modified epoxy can improve the heat resistance and moisture resistance by improving the plating adhesion and the ductility of the insulating layer when used as an insulating layer.
  • the urethane-modified epoxy resin examples include UME-315 (Kukdo Chemical), UME-330 (Kukdo Chemical) and the like, but are not limited thereto. At this time, these can be used individually or in mixture of 2 or more types.
  • the urethane-modified epoxy resin is preferred because the plating adhesion is excellent when the modification rate is about 5 to 30% and heat resistance and moisture resistance are further improved.
  • the epoxy equivalent and viscosity of the urethane-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, plating adhesion, heat resistance, and moisture resistance can be further improved. It is preferable.
  • Carboxyl terminated butadiene rubber is a rubber-modified epoxy resin that is added to improve the compatibility of rubber and epoxy. It provides oil adhesion, adhesive strength and impact resistance to sheets. Can play a role.
  • the content of the modified epoxy resin may be in the range of 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 30 parts by weight. Range, and more preferably 5 to 15 parts by weight.
  • the content of the modified epoxy resin is less than 5 parts by weight, coating properties and plating adhesion properties may be degraded.
  • the content of the modified epoxy resin is more than 40 parts by weight, the compatibility between the modified epoxy resin and the epoxy resin may be reduced, and the adhesion between the coated circuit board and the insulator may be reduced. Deterioration in resistance and heat resistance is expected.
  • thermosetting resin composition for insulating resin layer formation which concerns on this invention can further contain a flame retardant (e) as needed.
  • the flame retardant may be used without limitation conventional flame retardants known in the art, organic flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, flame retardants such as silicon-based flame retardants, metal hydroxides and the like are preferred.
  • the flame retardant may be included in the ratio of 5 to 40 parts by weight with respect to 10 to 60 parts by weight of the polyphenylene ether modified resin, preferably in the range of 5 to 30 parts by weight, more preferably in the range of 5 to 15 parts by weight. have. When it is contained in the said range, flame resistance is enough in a resin composition, and the heat resistance of hardened
  • thermosetting resin composition for insulating resin layer formation of this invention may further contain a hardening accelerator.
  • the curing accelerator may use an organometallic salt or organometallic complex including at least one metal selected from the group consisting of iron, copper, zinc, cobalt, lead, nickel, manganese, and tin.
  • organometallic salts or organometallic complexes examples include iron naphthenates, copper naphthenates, zinc naphthenates, cobalt naphthenates, nickel naphthenates, manganese naphthenates, tin naphthenates, zinc Octanoate, tin octanoate, iron octanoate, copper octanoate, zinc 2-ethylhexanate, lead acetylacetonate, cobalt acetylacetonate, or dibutyltin malate. It is not limited. In addition, these can be used 1 type or in mixture of 2 or more types.
  • the curing accelerator may be included in 0.01 to 1 parts by weight based on 10 to 60 parts by weight of polyphenylene ether, but is not limited thereto.
  • thermosetting resin composition for insulating resin layer formation of this invention may further contain additives, such as an inorganic filler.
  • the inorganic filler may be silica, alumina, aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, or titanate, but is not limited thereto.
  • the resin composition of the present invention is a flame retardant generally known in the art as needed, and other thermosetting resins and thermoplastic resins and oligomers thereof, which are not described above, as long as they do not impair the intrinsic properties of the resin composition.
  • additives such as polymers, solid rubber particles or ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents and the like.
  • 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.
  • a polyimide (PI) film is used as the base support film.
  • 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, and low thermal expansion rate. 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, and preferably in the range of 12.5 to 50 ⁇ 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 the heat
  • 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 adhesive layer is formed on one surface of the polyimide (PI) film, and is a layer for bonding the inner wiring board and the insulating resin sheet.
  • the adhesive layer is not particularly limited as long as it has heat resistance, flexibility, smoothness, low water absorption, excellent flexibility, and flame retardancy.
  • a conventional adhesive known in the art can be used without limitation, and for example, an epoxy adhesive, a rubber adhesive, a polyimide adhesive, a polyolefin adhesive, an acrylic adhesive, or the like can be used. Among these, an epoxy adhesive is preferable.
  • the adhesive may be mixed with a variety of materials to secure properties such as heat resistance, flexibility, flame retardancy, and the like, for example, a carboxyl group-containing acrylic resin, a carboxyl group-containing acrylonitrile-butadiene rubber, (meth) acrylic acid ester , (Meth) acrylonitrile, unsaturated carboxylic acids, and other components conventional in the art can be used without limitation.
  • the adhesive may be used by appropriately adding plasticizers, antioxidants, flame retardants, dispersants, viscosity regulators, leveling agents, or other conventional additives within a range that does not significantly impair the object and effect of the present invention. .
  • the thickness of the adhesive layer is not particularly limited, but may be, for example, in the range of 1 to 50 ⁇ m, and preferably in the range of 10 to 30 ⁇ m.
  • the adhesive layer according to the present invention is formed by disposing an adhesive film on one surface of a polyimide film, or laminating or directly coating an adhesive or an adhesive-containing composition on one surface of the polyimide film.
  • the adhesive film when the adhesive film is disposed, the adhesive is coated on a release paper having excellent peelability and then laminated on a polyimide film, or a carrier with an adhesive is laminated on one side of the polyimide film and pressed to press the adhesive polyimide. It may be formed by removing the carrier after transferring to the surface. In this case, the carrier surface to which the adhesive layer is attached may be a release treatment.
  • a roll coater for example, a roll coater, bar coater, coater coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray It can be performed by applying an adhesive-containing composition on a polyimide film with a coater or the like, and drying for 1 to 30 minutes at a temperature of 50 to 130 °C.
  • Examples of the organic solvent that can be used when preparing the adhesive-containing composition include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like.
  • Carboxols such as acetic acid ester, cellosolve, 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 adhesive layer is protected by a protective film in order to prevent surface damage, adhesion of foreign matters, and the like.
  • the protective film can be used such as conventional plastic film known in the art.
  • the thickness of the protective film may range from 1 to 40 ⁇ m, preferably from 10 to 30 ⁇ m.
  • the insulated resin sheet of this invention is a polyimide (PI) film mentioned above; An adhesive layer formed on one surface of the polyimide film; And an insulating resin layer formed on the other side of the polyimide film.
  • PI polyimide
  • the insulating resin sheet 100 of the present invention the polyimide film 120, the adhesive layer 110 located on one surface of the polyimide film; And an insulating resin layer 130 positioned on the other surface of the polyimide film, and have a structure in which they are sequentially stacked.
  • the polyimide film 120 not only serves to physically support the insulating resin sheet, but also has heat resistance and flexibility, thereby increasing the degree of freedom in product design.
  • the polyimide film may contain an inorganic filler, if necessary, to adjust the substrate thermal expansion coefficient (CTE).
  • the thickness of the polyimide film 120 may range from 5 ⁇ m to 100 ⁇ m, preferably 12.5 to 50 ⁇ m, and more preferably 12.5. To 25 ⁇ m.
  • the adhesive layer 110 is formed on the other side of the polyimide film 120, the insulating resin layer is not formed, and serves to bond the inner wiring board and the insulating resin sheet 100. do.
  • the thickness of the adhesive layer 100 is not particularly limited as long as it faithfully performs the aforementioned adhesive role, and may be, for example, in the range of 1 to 50 ⁇ m, and preferably in the range of 1 to 30 ⁇ m.
  • the adhesive layer 110 is preferably protected by a protective film for preventing damage to the surface, adhesion of foreign matters, and the like.
  • the protective film can be used such as conventional plastic film known in the art.
  • the thickness of the protective film may range from 1 to 40 ⁇ m, preferably from 10 to 30 ⁇ m.
  • the insulating resin layer 130 is disposed on the upper surface of the polyimide film 120, and includes a soluble material capable of forming roughness by a desmear process.
  • the thickness of the insulating resin layer 130 may be in the range of 1 to 50 ⁇ m, and preferably in the range of 1 to 30 ⁇ m, without affecting the substrate thermal expansion characteristics.
  • a film that can be peeled off after heating and pressing is applied during coating.
  • the insulating resin layer 130 includes a cured product layer formed by curing the above-mentioned thermosetting resin composition for forming an insulating resin layer, wherein the thermosetting resin composition does not necessarily need to be completely heat cured, and the effects of the present invention It should just be hard enough to be exhibited.
  • the cured product layer may be obtained by a method of heating and curing an adhesive sheet coated with a thermosetting resin composition on a support.
  • the adhesive sheet is coated with a thermosetting resin composition varnish for forming an insulating resin layer on a support and heated and dried, and then adhered to one side of the polyimide film, or heating, drying and curing the resin varnish applied on the support
  • the insulating resin layer can be obtained by simultaneously / sequentially carrying out, and this insulating resin layer can also be adhere
  • the insulating resin sheet 100 may further include a support layer 150 on the insulating resin layer 130.
  • 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.
  • the polyimide (PI) film When the polyimide (PI) film is used as the support, hot pressing at about 220 ° C. is possible. In the case of a polyethylene terephthalate (PET) film, a low-temperature press of about 180 ° C. may be used.
  • PET polyethylene terephthalate
  • a plastic film in order to be able to peel from the hardened
  • the plastic film may be a matte treatment or a corona treatment, and may form a release layer on the treatment surface.
  • metal foil can be removed by etching, when using metal foil as a support body, it is not necessary to use a release layer further. Moreover, it can also be used as a conductor layer, without peeling a metal foil. Examples of the metal foil that can be used include aluminum foil and copper foil, and when such a metal foil is used as a support layer, a hot press of about 220 ° C. is possible.
  • the thickness of the support layer 150 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 insulating resin sheet 100 may further include a release layer 140 between the insulating resin layer 130 and the support layer 150.
  • the release layer 140 When the release layer 140 separates the support layer 150 from the cured product of the thermosetting resin composition after pressing, the release layer 140 has a function of easily separating so that the insulating resin layer 120 can be maintained without being damaged.
  • the release layer may be a film type release material that is generally used.
  • the release agent used in the release layer 140 is not particularly limited, 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 thickness of the release layer 140 is not particularly limited, and may be, for example, in the range of 0.01 to 10 ⁇ m, preferably in the range of 0.1 to 5 ⁇ m.
  • the method of forming the release layer 140 is not specifically limited, A well-known method, such as a hot press, a hot roll lamination, extrusion lamination, coating application, drying, can be employ
  • the insulated resin sheet 100 which concerns on this invention can be obtained by adhering the insulated resin layer 130 which the said thermosetting resin composition hardened
  • FIG. For example, a method of laminating and bonding the insulating resin layer 130 composed of the support layer 150 and the cured product layer of the thermosetting resin composition to one side of the polyimide film 120, and the polyimide film 120 described above. Laminating and bonding to the insulating resin layer 130 and the like, the sheet-like insulating resin layer 130 and the polyimide film 120 may be wound in a roll shape, respectively, may be laminated in a continuous manner, and also roll type After cutting both sheets of lamination, lamination may be performed.
  • the total thickness of the adhesive layer 110, the polyimide film 120 and the insulating resin layer 130 is in the range of 10 ⁇ m to 200 ⁇ m, preferably in the range of 20 to 100 ⁇ m have.
  • the thickness of the insulated resin sheet falls within the above-mentioned range, the embedding of the circuit is sufficient and the thickness of the multilayer printed circuit board can be reduced.
  • the present invention includes a multilayer printed circuit board using the above-described insulating resin sheet as an insulating layer.
  • the multilayer printed circuit board refers to a printed circuit board laminated in two or more layers by a plating through hole method, a buildup method, or the like, and can be obtained by overlaying an insulating resin sheet on an inner wiring board and heating and pressing.
  • the multilayer printed circuit board may reduce the overall lamination thickness and the final product by using the insulating resin sheet according to the present invention, in which a polyimide film having flexibility and an insulating resin layer capable of forming roughness by a desmear process are sequentially laminated. It is possible to realize a high density microcircuit pattern while increasing the design freedom of the.
  • the printed circuit board of the present invention can be manufactured by conventional methods known in the art, for example, semi-additive, except for using the above-mentioned insulating resin sheet.
  • At least one insulating resin sheet is laminated on one or both surfaces of the inner layer wiring board, and the adhesive layer of the insulating resin sheet is placed in contact with the metal surface of the wiring board.
  • the step of forming an insulating layer through a heating, pressing process to build up the laminate (ii) forming at least one hole in the insulating layer of the laminate; (iii) desmearing the surface of the insulating layer and the inside of the hole to form roughness; (iv) forming an electroless plating layer on the roughness surface and the inner surface of the hole of the insulating layer; (v) forming a pattern using a photoresist on the formed electroless plating layer; (vi) forming a circuit layer on the pattern by electroplating; And (vii) exfoliating the photoresist and removing the exposed electroless plating layer.
  • the adhesive layer of the insulating resin sheet is placed in contact with the metal surface of the wiring board, and then heated and pressed to form a laminate (see Fig. 2 (a)).
  • the inner layer wiring board is used as a core substrate, and conventional ones known in the art may be used without limitation.
  • a double-sided flexible plate with flexible metal (FCCL) can be used.
  • FCCL flexible metal
  • a double-sided copper plate is drilled to form holes and plated, and then dry film resistors are laminated on both sides, and exposed, developed and etched to form a wiring pattern. It can be produced by press coating on the part.
  • the inner layer wiring board and the insulating resin sheet is laminated, but arranged to contact the metal layer of the inner layer wiring board and the adhesive layer of the insulating resin sheet and then using a vacuum pressurized laminator device or the like Vacuum heating press molding.
  • the protective film when the protective film is disposed on the adhesive layer of the insulating resin sheet, the protective film is removed, and then the exposed adhesive layer is disposed to contact the metal surface of the inner layer wiring board, followed by a heating and pressing process.
  • condition to heat press molding it does not specifically limit as a condition to heat press molding here, For example, it can carry out at the temperature of 60-160 degreeC, and a pressure of 0.2-3 MPa. Moreover, it does not specifically limit as a condition to heat, For example, it can carry out by temperature 140-240 degreeC and time 30-120 minutes.
  • the adhesive layer of the said insulated resin sheet is overlaid on the said inner layer wiring board, and this is heat-pressure-molded by a flat plate press apparatus etc.
  • a flat plate press apparatus it does not specifically limit as a condition to heat press molding here, For example, it can carry out at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa.
  • an insulating layer is formed simultaneously with heat press molding.
  • the insulating resin sheet includes the release layer 140, the support layer 150, or both, after forming a laminate in this step, a release layer, a support layer sequentially stacked on each of the upper and lower surfaces of the laminate After removing the layers or both, the following step 2) is performed (see FIG. 2 (b)).
  • Holes are formed by irradiating a laser to the insulating layer of the laminate.
  • the laser may be an excimer laser, a UV laser, a carbon dioxide (CO 2 ) laser, or the like.
  • the desmear process removes resin residues (smear) after laser irradiation by oxidizing agents such as permanganate, dichromate, etc.
  • oxidizing agents such as permanganate, dichromate, etc.
  • the surface of the insulating layer and the inner surface of the hole are processed by laser processing. An rough surface having an appropriate roughness (roughness) is formed.
  • the surface of the smooth insulating layer 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 layer after the desmear process.
  • the surface of the insulating layer after the desmear process has a desirable roughness for forming a fine circuit pattern.
  • the surface roughness range of the insulating layer 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 rough surface of the insulating layer and the inner surface of the hole (see FIG. 2 (e)).
  • Electroless plating is performed on the roughness surface and the inner surface of the hole to form a relatively thin plating layer.
  • the electroless plating layer is to secure the adhesive strength to the insulating resin 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 a photoresist (see FIG. 2 (f)).
  • 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 conductor layer for forming the fine circuit pattern in the opening of the photoresist layer is formed by electroplating.
  • the electroplating layer forms a new circuit layer connected to the inner layer wiring board by the hole.
  • the thickness of the electroplating layer is preferably in the range of about 1 ⁇ m to 100 ⁇ m.
  • circuit pattern is completed by removing the unnecessary photoresist layer and removing the exposed electroless plating layer.
  • the manufacturing of the printed circuit board 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 manufacturing method of the multilayer 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 polyphenylene ether modified resin, an epoxy resin, a curing agent, a modified epoxy resin, if necessary, a flame retardant was mixed to prepare a resin composition for forming an insulating resin layer.
  • the amount of each composition is used in parts by weight.
  • a B-stage form was formed by coating and drying an adhesive layer for adhesion with an inner wiring board on one side using an APICAL Polyimide film (12.5 ⁇ m) of Kaneka 12.5 NPI. Thereafter, the prepared resin composition was coated on the other side of the PI film using a gravure coater (Gravure Coater) to a thickness of 5 ⁇ m, and then dried by using a dryer at 150 ° C. for about 5 to 10 minutes.
  • a gravure coater Granure Coater
  • a multi-layer printed circuit board was manufactured by performing hole processing, desmear treatment, electroless plating layer, and circuit formation according to a conventional method.
  • Epoxy Resin 1 YD-011 (Epoxy Equivalent 500g / eq)
  • Epoxy Resin 2 YD-128 (Epoxy Equivalent 190g / eq)
  • Modified epoxy resin 1 Dimer acid modified epoxy resin (KSR-200)
  • Modified epoxy resin 2 Urethane modified epoxy resin (UME-315)
  • Flexibility The copper foil of the produced laminated sheet was removed by etching, and bent to the obtained insulating layer, and flexibility was evaluated by the presence or absence of fracture at that time. A: No fracture, B: Fine fracture phenomenon , C: breaking
  • Ra value was measured using a non-contact 3D Optical Profiler (Bruker Contour GT) to measure the surface roughness.
  • the Ra value is an average value of the heights calculated over the entire measurement area. Specifically, the absolute value of the height that changes in the measurement area is measured and arithmetic averaged from the surface of the average line.
  • the average roughness of 10 points It is the value measured according to the calculation.
  • the printed circuit board using the insulating resin sheet of the present invention was less than half the level of the surface roughness after the desmear treatment, and showed excellent characteristics in flammability, plating adhesion, and heat resistance (see Table 1). ).
  • the multilayered printed circuit board with high reliability can be manufactured in the future, and it is judged to be useful as a constituent material of a small and lightweight new semiconductor package.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de résine isolante comportant un film de polyimide, une couche d'adhésion réalisée sur une face du film de polyimide, et une résine isolante réalisée sur l'autre face du film de polyimide de façon que la rugosité puisse être obtenue par déglaçage. L'invention concerne également, d'une part une carte de circuits imprimés multicouche comportant la feuille de résine isolante, et d'autre part un procédé de fabrication destiné à ladite carte de circuits imprimés. L'invention permet ainsi la réalisation d'une carte de circuits imprimés par accumulations successives, ce qui permet de réduire l'épaisseur d'ensemble des couches, de laisser plus de liberté pour concevoir un substrat, et de réaliser un tracé de microcircuits de haute densité.
PCT/KR2013/011395 2012-12-10 2013-12-10 Carte de circuits imprimés multicouche, et procédé de fabrication correspondant Ceased WO2014092428A1 (fr)

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KR1020120142976A KR101420939B1 (ko) 2012-12-10 2012-12-10 다층 인쇄 회로 기판 및 그 제조 방법
KR10-2012-0142976 2012-12-10

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KR101676119B1 (ko) * 2014-12-01 2016-11-14 주식회사 두산 연성 인쇄회로기판 형성용 절연 수지 시트 및 이의 제조방법, 이를 포함하는 인쇄회로기판

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006224644A (ja) * 2005-01-18 2006-08-31 Kaneka Corp 絶縁シートおよび金属層／絶縁シート積層体とそれを用いたプリント配線板
KR100835785B1 (ko) * 2007-06-26 2008-06-09 주식회사 두산 인쇄회로기판용 수지 조성물, 이를 이용한 복합기재 및동박 적층판
KR20110008044A (ko) * 2008-03-25 2011-01-25 아지노모토 가부시키가이샤 절연 수지 시트 및 상기 절연 수지 시트를 사용한 다층 프린트 배선판의 제조 방법
JP2011105916A (ja) * 2009-11-20 2011-06-02 Kyocera Chemical Corp プリプレグ、多層プリント配線板およびフレキシブルプリント配線板
KR20120024417A (ko) * 2010-08-11 2012-03-14 아지노모토 가부시키가이샤 적층판의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006224644A (ja) * 2005-01-18 2006-08-31 Kaneka Corp 絶縁シートおよび金属層／絶縁シート積層体とそれを用いたプリント配線板
KR100835785B1 (ko) * 2007-06-26 2008-06-09 주식회사 두산 인쇄회로기판용 수지 조성물, 이를 이용한 복합기재 및동박 적층판
KR20110008044A (ko) * 2008-03-25 2011-01-25 아지노모토 가부시키가이샤 절연 수지 시트 및 상기 절연 수지 시트를 사용한 다층 프린트 배선판의 제조 방법
JP2011105916A (ja) * 2009-11-20 2011-06-02 Kyocera Chemical Corp プリプレグ、多層プリント配線板およびフレキシブルプリント配線板
KR20120024417A (ko) * 2010-08-11 2012-03-14 아지노모토 가부시키가이샤 적층판의 제조 방법

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