WO2014109593A1 - Film isolant de résine, substrat comprenant une couche métallique mince, carte de circuit imprimé comprenant un film isolant de résine et procédé de fabrication de carte de circuit imprimé comprenant un film isolant de résine - Google Patents

Film isolant de résine, substrat comprenant une couche métallique mince, carte de circuit imprimé comprenant un film isolant de résine et procédé de fabrication de carte de circuit imprimé comprenant un film isolant de résine Download PDF

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Publication number
WO2014109593A1
WO2014109593A1 PCT/KR2014/000311 KR2014000311W WO2014109593A1 WO 2014109593 A1 WO2014109593 A1 WO 2014109593A1 KR 2014000311 W KR2014000311 W KR 2014000311W WO 2014109593 A1 WO2014109593 A1 WO 2014109593A1
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WIPO (PCT)
Prior art keywords
layer
insulating
forming
insulating resin
hole
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Ceased
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PCT/KR2014/000311
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English (en)
Korean (ko)
Inventor
이현진
남동기
박한성
유의덕
김우정
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Doosan Corp
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Doosan Corp
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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
    • H05K1/0373—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
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • 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
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0212—Resin particles
    • 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
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0191—Using tape or non-metallic foil in a process, e.g. during filling of a hole with conductive paste
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0773—Dissolving the filler without dissolving the matrix material; Dissolving the matrix material without dissolving the filler
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/426—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in substrates without metal
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/427—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in metal-clad substrates

Definitions

  • the present invention relates to an insulating resin film capable of improving adhesion strength with a plating layer in a printed circuit board, a metal foil laminate and a printed circuit board including the insulating resin film, and a method of manufacturing a printed circuit board using the insulating resin film.
  • a subtractive process in which a part of a metal foil of a copper clad laminate (CCL) is etched to form a circuit by etching.
  • CCL copper clad laminate
  • Such a subtractive method is widely used because a large area can be collectively processed and the management of etching liquid is relatively easy and inexpensive.
  • the obtained circuit cross section becomes a trapezoid having a wide bottom and the etching resist after the process is completed. There is a difference between the width and the width of the actual pattern.
  • the trapezoidal circuit due to the trapezoidal circuit, the mounting area is narrowed, and thus, the mounting reliability is deteriorated and problems such as poor bonding occur. Therefore, there is a limit in forming a fine circuit through the subtractive method.
  • the semi-additive method is a wiring formation method combining a subtractive method of forming a circuit pattern by etching and an additive method of forming a circuit by plating only a pattern portion, and the cross section of the circuit obtained is Since it becomes substantially rectangular, a fine circuit can be formed precisely.
  • a metal foil laminate in which a prepreg 1, a primer 2, and a copper foil 3 are sequentially stacked is prepared.
  • the copper foil 3 is removed by etching the entire copper foil of the prepared metal foil laminate, roughness is formed on the surface of the primer 2.
  • the photoresist 5 was laminated thereon, and then a part of the photoresist 5 was removed. It is selectively removed to expose a portion of the copper seed layer 4.
  • electrolytic copper plating is formed on a part of the exposed metal seed layer 4 to form an electrolytic copper plating layer 6, and then the photoresist 5 is removed to etch the exposed copper seed layer 5 through etching. By removing it, a printed circuit board can be manufactured.
  • the adhesive strength of the circuit largely depends on the adhesive strength between the copper seed layer and the primer (insulating layer).
  • the copper seed layer of the rough surface portion of the primer may not be removed properly, and the rough surface portion Etching under conditions capable of sufficiently removing the copper seed layer may not only dissolve the electrolytic copper plating layer and make it fine circuitry, but also under-cut the copper seed layer of the portion where the copper plating layer is formed and insulate the copper seed layer.
  • the adhesive strength between an electrolytic copper plating layer and an insulating layer falls by lowering the adhesive strength between layers.
  • via holes to be used in the inner layer of the double-sided flexible printed circuit board or multilayer flexible printed circuit board
  • Various methods have been developed, such as manufacturing the formed flexible printed circuit boards by sheet or roll-to-roll method.
  • Korean Patent Publication No. 10-2011-0026128 discloses a method of manufacturing a flexible printed circuit board using a sputtering method. This sputtering method is advantageous for the formation of fine circuit patterns and the formation of via holes, but it tends to have poor adhesion reliability compared to conventional subtractive methods or semi-additive methods. In particular, it is vulnerable to high temperature adhesion reliability.
  • An object of the present invention is to provide an insulating resin film and a metal foil laminate comprising the insulating resin film capable of forming roughness by desmear treatment while maintaining high electrical insulation and heat resistance to improve adhesive strength with a plating layer. do.
  • the present invention includes an insulating layer formed by using the insulating resin film, excellent electrical insulation and heat resistance, and improved adhesion strength between the insulating layer and the plating layer and a printed circuit board and a method of manufacturing the same, the fine circuit pattern is implemented To provide another purpose.
  • the present invention provides an insulating resin film that can improve the adhesive strength with the plating layer in the printed circuit board.
  • the insulating resin film is a polyimide resin; And an insulating resin layer uniformly dispersed in the polyimide resin and containing a plurality of rubber particles that can be removed by a desmear treatment.
  • the polyimide resin layer may be laminated on one surface of the insulating resin layer.
  • a peelable release liner layer may be stacked on one surface of the insulating resin film.
  • the insulating resin film is a polyimide resin; And an insulating resin layer uniformly dispersed in the polyimide resin and containing a plurality of silica particles that can be removed by a desmear treatment or an aqueous alkali solution treatment.
  • the polyimide resin layer may be laminated on one surface of the insulating resin layer.
  • a peelable release liner layer may be stacked on one surface of the insulating resin film.
  • the present invention is a metal foil; And an insulating layer formed by laminating one or more insulating resin films on one surface of the metal foil.
  • the present invention provides a printed circuit board including an insulating layer formed by laminating one or more insulating resin films described above.
  • the printed circuit board is formed by laminating one or more insulating resin films, and is an insulating layer having one or more holes formed therein, wherein rubber particles or silica particles are removed from a surface and an inner wall surface of the hole.
  • the printed circuit board is a metal foil; At least one insulating resin film is laminated on one surface of the metal foil, and is an insulating layer having one or more first holes formed therein, and a roughness surface formed by removing rubber particles or silica particles from a surface and an inner wall surface of the first hole. Insulating layer comprising; A metal seed layer formed on the rough surface; And a plating layer formed on the metal seed layer.
  • the present invention provides a method of manufacturing the printed circuit board.
  • the manufacturing method comprises the steps of forming one or more holes in the insulating layer formed by laminating one or more insulating resin film; Removing the rubber particles on the surface of the insulating layer and the inner wall of the hole by a desmear process to form a roughness surface; Forming a metal seed layer on the rough surface; And forming a plating layer on the metal seed layer.
  • the manufacturing method comprises the steps of forming an insulating layer by laminating one or more insulating resin film on a metal foil; Forming at least one first hole in the insulating layer; Removing the rubber particles on the surface of the insulating layer and the inner wall of the first hole by a desmear process to form a roughness surface; Stacking a protective film layer on an opposite side of the metal foil on which the insulating layer is laminated; Forming a metal seed layer on the rough surface; And forming a plating layer on the metal seed layer.
  • the manufacturing method comprises the steps of forming one or more holes in the insulating layer formed by laminating one or more insulating resin film; Forming a roughness surface by removing silica particles on the surface of the insulating layer and the inner wall of the hole by a desmear treatment or an aqueous alkali solution; Forming a metal seed layer on the rough surface; And forming a plating layer on the metal seed layer.
  • the manufacturing method comprises the steps of laminating at least one insulating resin film on a metal foil to form an insulating layer; Forming at least one first hole in the insulating layer; Forming a rough surface by removing silica particles on the surface of the insulating layer and the inner wall of the first hole by a desmear treatment or an aqueous alkali solution; Stacking a protective film layer on an opposite side of the metal foil on which the insulating layer is laminated; Forming a metal seed layer on the rough surface; And forming a plating layer on the metal seed layer.
  • each step of each manufacturing method may be performed in a continuous process by a roll-to-roll method.
  • the insulating layer of the printed circuit board is used. As well as maintaining the heat resistance, the adhesion strength with the plating layer may be improved, and thus a precise circuit pattern may be implemented.
  • FIG. 1 is a cross-sectional view schematically illustrating a process of forming a fine circuit pattern of a printed circuit board through a general semi-additive process.
  • FIGS. 2 to 4 are cross-sectional views showing insulating resin films of various structures according to an example of the present invention.
  • 5 to 7 are cross-sectional views showing insulating resin films of various structures according to another example of the present invention.
  • FIG 8 and 9 are cross-sectional views showing metal foil laminates of various structures according to an example of the present invention.
  • FIGS 10 and 11 are cross-sectional views showing metal foil laminates of various structures according to another example of the present invention.
  • FIGS. 12 to 14 are cross-sectional views of a printed circuit board including an insulating resin film having various structures according to the present invention.
  • 15 to 18 are cross-sectional views schematically illustrating a process of manufacturing a printed circuit board using an insulating resin film having various structures according to the present invention as an insulating layer.
  • 100 insulation layer
  • 100A roughness plane
  • the present invention is an insulating resin film capable of forming an insulating layer in the manufacture of a printed circuit board, wherein the rubber particles removable by the desmear treatment are uniformly dispersed in the polyimide resin, or the desmear treatment is carried out in the polyimide resin.
  • Silica particles removable by the aqueous alkali solution is characterized in that it comprises an insulating resin layer is uniformly dispersed.
  • the insulating resin film is a polyimide resin (11); And an insulating resin layer 10 containing a plurality of rubber particles 12 that can be removed by a desmear treatment.
  • FIG. 5 to 7 are cross-sectional views of an insulating resin film according to another example of the present invention, wherein the insulating resin film comprises a polyimide resin (11); And an insulating resin layer 10 containing a plurality of silica particles 13 that can be removed by a desmear treatment or an aqueous alkali solution treatment.
  • the insulating resin film comprises a polyimide resin (11);
  • an insulating resin layer 10 containing a plurality of silica particles 13 that can be removed by a desmear treatment or an aqueous alkali solution treatment are cross-sectional views of an insulating resin film according to another example of the present invention, wherein the insulating resin film comprises a polyimide resin (11); And an insulating resin layer 10 containing a plurality of silica particles 13 that can be removed by a desmear treatment or an aqueous alkali solution treatment.
  • the insulating resin layer 10 may be uniformly dispersed in the polyimide resin 11 with the removable rubber particles 12 by desmear treatment, or may be subjected to the desmear treatment or alkaline aqueous solution treatment in the polyimide resin 11.
  • the removable silica particles 13 are uniformly dispersed.
  • rubber particles existing on the surface of the insulating resin layer may be removed by desmear treatment, or may be insulated water by desmear treatment or alkaline aqueous solution treatment. Silica particles present on the surface of the ground layer can be easily removed.
  • the metal component of the metal seed layer fills the groove of the roughness surface to form the metal seed layer on the surface of the insulating layer.
  • the groove portion filled with the metal component not only increases the adhesion surface area of the metal seed layer and the insulating layer, but also exhibits an anchor effect, the adhesive strength between the metal seed layer and the insulating layer may be significantly increased. Can be. Therefore, the fine circuit pattern can be easily implemented while improving the adhesive strength between the insulating layer and the plating layer.
  • the polyimide resin 11 is a polymer material having an imide ring, and exhibits excellent heat resistance, chemical resistance, abrasion resistance and weather resistance based on the chemical stability of the imide ring, and low thermal expansion coefficient. Low breathability and excellent electrical properties.
  • the polyimide is generally synthesized by condensation polymerization of an aromatic dianhydride and an aromatic diamine, and may be used without particular limitation as long as it is a polyimide known in the art.
  • the plurality of rubber particles 12 or silica particles 13 are uniformly dispersed in the entire polyimide resin 11 of the insulating resin layer 10.
  • the rubber particles 12 may be dissolved and removed by a desmear treatment, and the silica particles 13 may be dissolved and removed by a desmear treatment or an aqueous alkali solution treatment. Therefore, the rubber particles 12 present on the surface of the insulating resin layer 10 during the manufacture of the printed circuit board are removed by the desmear treatment, or the silica particles 13 are removed by the desmear treatment or the aqueous alkali solution treatment. As a result, as shown in FIGS.
  • fine grooves are formed on the surface of the insulating resin layer, and these fine grooves are filled with metal components of the metal seed layer by electroless chemical copper, sputtering, or the like, and serve as anchors.
  • the insulating resin layer and the metal seed layer are not only chemically bonded but also physically bonded, thereby significantly improving the adhesive strength.
  • the rubber particles 12 usable in the present invention are not particularly limited as long as they are known in the art as long as they are in the form of particles.
  • Examples of the synthetic rubber include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, styrene-acrylonitrile rubber, chloroprene rubber, isoprene rubber, isobutylene-isoprene rubber, Isobutylene-isoprene rubber, ethylene propylene rubber, ethylene vinyl acetate rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, ethylene acrylate rubber, fluorine rubber, silicone rubber, polyurethane, etc. . These may be used alone or in combination of two or more thereof.
  • the structure of the rubber particles may be a structure consisting of only the rubber particles themselves, or may be a core-shell structure including a rubber particle core and a shell layer of a heat resistant polymer on the core surface.
  • the rubber particles are preferable because of excellent heat resistance at the time of preparing the insulating resin film at a high temperature of 350 ° C. or higher.
  • the heat-resistant polymer is not particularly limited as long as it is known in the art as a resin that can withstand a long time at a high temperature of about 200 ⁇ 350 °C or more, and non-limiting examples include polymethacrylimide (PMI), acrylic resin, polyamide , Polyimide, polyamideimide, poly (meth-phenylene isophthalamide), polysulfone, polyetherketone, polyether imide, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polytetrafluoro Ethylene, polydiphenoxyphosphazene, polystyrene, polyacrylonitrile and the like.
  • PMI polymethacrylimide
  • acrylic resin polyamide
  • Polyimide polyamideimide
  • polysulfone polyetherketone
  • polyether imide polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate
  • the size of the rubber particles is not particularly limited, but the roughness of the insulating layer may vary depending on the size of the rubber particles, which may affect the adhesion strength and the microcircuit pattern implementation between the insulating layer and the plating layer. Therefore, when the size (particle diameter) of the rubber particles is adjusted in the range of nanoscale to several micrometers, preferably in the range of about 10 nm to 3 ⁇ m, the roughness Ra of the insulating layer is about 10 to 1000 nm, preferably about 100 to 500 nm, more preferably about 200 to 400 nm, while improving the adhesive strength between the insulating layer and the plating layer, a fine circuit pattern can be implemented.
  • the content of the rubber particles 12 is not particularly limited, but between rubber particles dispersed in the width of the circuit or the polyimide resin of the film in order to implement a microcircuit pattern while preventing a short circuit between circuits.
  • the content of the rubber particles is lower than 5 parts by weight, the roughness may not be properly formed during the manufacturing of the printed circuit board may cause a decrease in plating adhesion and high temperature adhesion.
  • silica particles 13 usable in the present invention are not particularly limited as long as they are in the form of particles of silica (SiO 2 ) known in the art.
  • the size (particle diameter) of the silica particles is not particularly limited as in the above-described rubber particles, but the size of the silica particles may affect the roughness of the insulating layer. Therefore, when the size (particle diameter) of the silica particles is adjusted within the range of nanoscale to several micrometers, preferably in the range of about 10 nm to 3 ⁇ m, the roughness Ra of the insulating layer is about 10 to 1000 nm, preferably about 100 to 500 nm, more preferably about 200 to 400 nm, the adhesion strength between the insulating layer and the plating layer is improved, a fine circuit pattern can be implemented.
  • the content of the silica particles is not particularly limited, but the width of the circuit, the spacing between the particles dispersed in the polyimide resin of the film, the size of the particles in order to implement a microcircuit while preventing short circuits between circuits. In consideration of the above, it is preferable to adjust the amount within the range of more than 5 parts by weight, less than 40 parts by weight, preferably 7 parts by weight or more and 35 parts by weight or less, based on 100 parts by weight of the polyimide resin, respectively. If the silica particle content is 40 parts by weight or more, the micro crack may occur, and dust of the silica particles distributed in the polyimide resin may be generated during the drilling process, thereby reducing the PCB defect rate. Can be increased. On the other hand, when the content of the silica particles is lower than 5 parts by weight, the roughness may not be properly formed during the manufacturing of the printed circuit board may cause a decrease in plating adhesion and high temperature adhesion.
  • the thickness of the insulating resin layer is not particularly limited, but may be in the range of about 1 to 30 ⁇ m.
  • the insulating resin film according to the present invention may further include an additive such as an inorganic filler, a plasticizer, an antioxidant, a flame retardant, etc., in addition to the polyimide resin and rubber particles (or silica particles) in the insulating resin layer 10.
  • an additive such as an inorganic filler, a plasticizer, an antioxidant, a flame retardant, etc.
  • the content of the additive is not particularly limited, and may be about 0.001 to 10 parts by weight based on 100 parts by weight of the polyimide resin.
  • the inorganic filler serves to reduce the difference in coefficient of thermal expansion (CTE) between the insulating layer and the plating layer formed of the insulating resin film or the difference in the coefficient of thermal expansion between the insulating layer and the metal foil.
  • CTE coefficient of thermal expansion
  • Non-limiting examples of such inorganic fillers are talc, mica, silica, calcium carbonate, magnesium carbonate, clay, calcium silicate, titanium oxide, antimony oxide, glass fibers or their Mixtures and the like.
  • the content of the inorganic filler is not particularly limited, and for example, about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the polyimide resin.
  • the insulating resin composition includes silica, it is appropriate to use a material different from silica as the inorganic filler.
  • the polyimide resin layer 20 may be stacked on one surface of the insulating resin layer 10.
  • the mechanical strength of the insulating resin layer can be complemented by the polyimide resin layer, so that the mechanical strength is further maintained while maintaining excellent adhesion between the insulating layer and the plating layer of the printed circuit board. Can be improved.
  • a release liner layer 30 may be stacked on one surface of the insulating resin film.
  • the release liner layer 30 As described above, the insulating resin film can be protected from external contamination. However, when the insulating resin film is applied to the printed circuit board, the release liner layer is removed.
  • the release liner layer 30 may be a plastic film or the like, which may be release treated or have a low surface energy, and may be peeled off.
  • the release liner layer 30 is a peelable and heat resistant plastic film.
  • the insulating resin film of the present invention can be produced by a variety of methods. However, it is not limited to the following method.
  • the insulating resin film is a polyamic acid solution or a liquid polyimide resin; Applying an insulating resin composition comprising a rubber particle removable by a desmear treatment or a silica particle removable by a desmear treatment or an aqueous alkali solution treatment, onto a peelable release liner layer and then curing to form an insulating resin layer It can be prepared by a method comprising. At this time, the peelable release liner layer is removed during use.
  • the method for producing the insulating resin film is a step of forming a polyimide resin layer by applying the polyamic acid solution or a liquid polyimide resin on the formed insulating resin layer and then cured It may further include.
  • an insulating resin layer is formed on the release liner layer that can be peeled off (hereinafter, 'S10 step').
  • an insulating resin composition is prepared by mixing a polyamic acid solution or a liquid polyimide resin prepared by dissolving an aromatic dianhydride and an aromatic diamine in a polar solvent with rubber particles or silica particles, and then releasing the insulating resin composition.
  • the insulating resin layer may be formed on the release liner by applying it on the liner and curing by applying heat.
  • the insulating resin composition used in the present invention comprises (a) a polyamic acid solution or a polyimide resin solution, and (b) rubber particles removable by desmear treatment, or silica particles removable by desmear treatment or aqueous alkali solution treatment. Include.
  • the polyamic acid solution is obtained through the imidization reaction of dianhydride and diamine, thereby preparing a polyimide resin.
  • Non-limiting examples of aromatic dianhydrides used in the preparation of the polyamic acid include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic Dianhydrides (BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride), 3,3', 4,4'-benzophenonethene carboxylic dianhydride (BTDA: 3,3 ', 4, 4'-benzophenonetetracarboxylic dianhydride), 4,4'-oxydiphthalic anhydride (ODPA: 4,4'-oxydiphthalic anhydride), 4,4 '-(4,4'-isopropylidenediphenoxy) -bis -(Phthalic anhydride) (BPADA: 4,4'-isopropylidenediphenoxy) -bis (phthalic anhydride), 2,2'-bis- (3,4-dicarboxyphenyl) hexa
  • non-limiting examples of the diamine include p-phenylene diamine (p-PDA: p-phenylene diamine), m-phenylene diamine (m-PDA: m-phenylene diamine), 4,4'-oxydianiline (4,4'-ODA: 3,4'-oxydianiline), 2,2-bis (4-4 [aminophenoxy] -phenyl) propane (BAPP: 2,2-bis (4- [4-aminophenoxy] phenyl) propane), 2,2'-dimethyl-4,4'-diamino biphenyl (m-TB-HG: 2,2'-Dimethyl-4,4'-diaminobiphenyl), 1,3-bis ( 4-aminophenoxy) benzene (TPER: 1,3-bis (4-aminophenoxy) benzene), 2,2-bis (4- [3-aminophenoxy] phenyl) sulfone (m-BAPS: 2,2- bis (4- [3-aminophenoxy
  • Non-limiting examples of the solvent used to prepare the polyamic acid solution include N-methylpyrrolidinone (NMP: N-methylpyrrolidinone), N, N-dimethylacetamide (DMAc: N, N-dimethylacetamide), tetrahydrofuran (THF: tetrahydrofuran), N, N-dimethylformamide (DMF: N, N-dimethylformamide), dimethyl sulfoxide (DMSO: dimethylsulfoxide), cyclohexane, acetonitrile and the like. These may be used alone or in combination of two or more thereof.
  • NMP N-methylpyrrolidinone
  • DMAc N, N-dimethylacetamide
  • THF tetrahydrofuran
  • N, N-dimethylformamide N, N-dimethylformamide
  • DMSO dimethylsulfoxide
  • cyclohexane acetonitrile and the like.
  • 'polyimide resin solution' a plurality of rubber particles dissolved and removed by desmear treatment are mixed, or desmear treatment or aqueous alkali treatment. It is possible to prepare an insulating resin composition by mixing the silica particles dissolved and removed by. At this time, it is preferable to stir so that the rubber particles or silica particles are uniformly dispersed throughout the polyamic acid solution or the polyimide resin solution.
  • the content of the rubber particles and the silica particles is not particularly limited, and more than 5 parts by weight, less than 40 parts by weight, preferably 7 parts by weight or more, 35 parts by weight based on 100 parts by weight of the liquid polyimide resin (or polyamic acid solution), respectively. Or less.
  • the insulating resin composition in addition to the polyamic acid solution, the polyimide resin solution, the rubber particles or the silica particles within a range that does not significantly impair the object and effect of the present invention, inorganic fillers, plasticizers, antioxidants, flame retardants, It may further include additives such as a dispersant, a viscosity modifier, a leveling agent.
  • the content of the additive is not particularly limited, and may be about 0.001 to 10 parts by weight based on 100 parts by weight of the liquid polyimide resin (or polyamic acid solution).
  • the content of the inorganic filler may be about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, more preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the liquid polyimide resin (or polyamic acid solution). .
  • the viscosity of the insulating resin composition is not particularly limited, but is in the range of about 1,000 to 50,000 cps, preferably in the range of about 1,000 to 30,000 cps, more preferably in the range of about 2,000 to 30,000 cps, even more preferably about 10,000 To 30,000 cps.
  • the thickness of the insulating resin composition to be applied may vary depending on the concentration, but after the curing reaction (imidation reaction) is finished, It is desirable to adjust the thickness so that it is about 2 to 30 mu m. If the thickness of the insulating resin layer is more than about 30 ⁇ m conflict with the purpose of thinning the device.
  • the prepared insulating resin composition When the prepared insulating resin composition is applied to a release liner and then heated, the aromatic dianhydride and the aromatic diamine are imidized to form an insulating resin layer on the release liner.
  • the heating temperature may be about 150 to 700 °C
  • heating time may range from 5 minutes to 1 hour, but is not limited thereto.
  • the polyimide resin layer and the second insulating resin layer may be sequentially formed on the insulating resin layer formed in step S10.
  • the polyimide resin layer is formed by applying the polyamic acid solution or the liquid polyimide resin and then applying heat to cure ('S20 step').
  • the polyamic acid solution or polyimide resin solution usable in this step may be the same as the polyamic acid solution or polyimide resin solution used in step S10.
  • additives may be added to the polyamic acid solution or the polyimide resin solution as necessary.
  • the additives include inorganic fillers, plasticizers, antioxidants, flame retardants, dispersants, viscosity modifiers, leveling agents, and the like.
  • the inorganic filler is the same as the type of inorganic filler that can be added to the insulating resin composition in the step S10.
  • the content of the inorganic filler may be about 10 to 20 parts by weight based on the total weight of the polyamic acid solution or the polyimide resin solution.
  • the viscosity of the polyamic acid solution or the polyimide resin solution is not particularly limited, but may be in the range of about 1,000 to 50,000 cps.
  • the thickness of the polyamic acid solution or the polyimide resin solution to be applied may vary depending on the concentration, but finally the curing reaction (imidization reaction) is finished. It is preferable to adjust so that the thickness of a polyimide resin layer may be about 1-30 micrometers.
  • the second insulating resin layer is formed by coating and then curing the insulating resin composition on the polyimide resin layer formed in step S20 ('S30 step').
  • the component of the insulating resin composition is the same as the component of the insulating resin composition used in step S10.
  • the insulating resin film is a step of applying the insulating resin composition on the release liner layer that can be peeled and then cured to form an insulating resin layer; Applying the polyamic acid solution or the liquid polyimide resin onto a release liner layer and then curing to form a polyimide resin layer;
  • the insulating resin layer and the polyimide resin layer may be prepared by a method comprising the step of laminating these layers in contact.
  • the components and viscosity, the coating thickness, the heating temperature and the time of the insulating resin composition, the polyamic acid solution and the polyimide resin solution used in the above method are the same as in the above-mentioned manufacturing method.
  • the method of laminating the insulating resin layer and the polyimide resin layer is not particularly limited as long as it is known in the art, but when using the roll-to-roll method, a large area insulating resin film is a simple process. It is preferable because it can be easily manufactured through.
  • the present invention provides a metal foil laminate comprising the insulating resin film described above.
  • the insulating resin film By including the insulating resin film with a metal foil laminate, the high electrical insulation and heat resistance of the insulating layer may be maintained when manufacturing the printed circuit board, and the fine circuit pattern may be formed while improving the adhesive strength between the insulating layer and the plating layer.
  • the metal foil laminate is a metal foil 40; And an insulating layer 100 formed by laminating one or more insulating resin films on one surface of the metal foil.
  • the insulating resin film is selected from the insulating resin film shown in Figures 2 to 7, can be used alone or two or more kinds of films. However, when there is a release liner layer 30 as shown in FIGS. 4 and 7, the release liner layer is removed and used. If the insulating resin film of FIG. 3 or 6 is used, as shown in FIGS. 9 and 11, the polyimide resin layer 20 and the insulating resin layer 10 are sequentially stacked on the metal foil 40. An insulating layer 100 of the insulating resin film may be formed.
  • the metal foil 40 is not particularly limited as long as it is a metal having conductivity and ductility.
  • One example of the metal foil may be copper, tin, gold, or silver, and preferably copper. In the case of copper foil, it may be a rolled copper foil or an electrolytic copper foil.
  • the thickness of the metal foil 40 is not particularly limited, but may be in the range of about 5 to 40 ⁇ m, and preferably in the range of about 9 to 35 ⁇ m.
  • the manufacturing method of the metal foil laminate is as follows, but is not limited thereto.
  • the method for producing a metal foil laminate is applied to the insulating resin composition used in the step S10 when manufacturing the insulating resin film on the metal foil, and then applied to the applied insulating resin composition to cure the insulating layer It may include forming a.
  • the polyamic acid solution or polyimide resin solution used in step S20 at the time of preparing the insulating resin film is applied onto the metal foil, and then the applied polyamic acid solution. Or hardening by applying heat to the polyimide resin solution to form a polyimide resin layer; And applying the insulating resin composition used in the step S10 in the preparation of the above insulating resin film on the polyimide resin layer, and then applying heat to the applied insulating resin composition to form an insulating layer.
  • the polyamic acid solution or polyimide resin solution used in step S20 at the time of preparing the insulating resin film is applied onto the metal foil, and then the applied polyamic acid solution. Or hardening by applying heat to the polyimide resin solution to form a polyimide resin layer; And applying the insulating resin composition used in the step S10 in the preparation of the above insulating resin film on the polyimide resin layer, and then applying heat to the applied insulating resin composition to form an insulating layer.
  • the components and viscosity, the coating thickness, the heating temperature and the time of the insulating resin composition, the polyamic acid solution and the polyimide resin solution are all the same as the preparation of the insulating resin film described above.
  • the present invention provides a printed circuit board comprising the insulating resin film described above.
  • the printed circuit board is insulated in which rubber particles removable by the desmear process are uniformly dispersed in the polyimide resin, or silica particles removable by desmear treatment or aqueous alkali solution are uniformly dispersed in the polyimide resin.
  • the printed circuit board according to the present invention includes an insulating layer formed by laminating one or more insulating resin films.
  • FIG. 12 is a cross-sectional view of a printed circuit board according to an exemplary embodiment of the present invention, wherein the printed circuit board includes an insulating layer 100, a metal seed layer 200, and a plating layer 300.
  • the present invention is not limited thereto.
  • the insulating layer 100 is formed of one selected from the insulating resin film shown in FIGS.
  • the insulating layer 100 may include a plurality of rubber particles that can be removed by a desmear treatment or a plurality of silica particles that can be removed by a desmear treatment or an aqueous alkali solution. It may be formed of an insulating resin film including the insulating resin layer 10 uniformly dispersed in the mid resin. In some cases, the insulating layer 10 may be formed using an insulating resin film in which the polyimide resin layer 20 is laminated on one surface of the insulating resin layer 10 (not shown).
  • One or more holes 110 are formed in the insulating layer 100.
  • rough surface (100A) rubber particles are removed by the desmear treatment or silica particles are removed by the desmear treatment or the aqueous alkali solution treatment on the surface of the insulating layer and the inner wall surface of the hole, thereby forming a plurality of fine grooves. It is referred to as rough surface (100A).
  • the groove of the rough surface 100A may be filled with a metal component when forming a metal seed layer by an electroless chemical copper plating method of a printed circuit board to act as an anchor. As a result, the adhesion between the insulating layer and the metal seed layer formed below may be increased.
  • the roughness Ra of the roughness plane 100A depends on the size of the rubber particles, which ranges from several nm to several ⁇ m, preferably from about 10 to 1000 nm, more preferably from about 100 to 500 nm, even more preferably. In the range of about 200 to 400 nm, the adhesive strength between the insulating layer 100 and the metal seed layer may be increased, thereby increasing the adhesion between the insulating layer and the conductive layer.
  • the metal seed layer 200 is formed on the surface of the insulating layer 100 and the inner wall surface of the hole 110.
  • the metal seed layer 200 is formed while the groove of the roughness surface 100A is filled with a metal component.
  • the groove filled with the metal component acts as an anchor, and the metal seed layer 200 is chemically and physically bonded to the rough surface 100A by the anchor, such that the metal seed layer 200 and the insulating layer 100 are formed.
  • the adhesion between the plating layer 300 and the insulating layer 100 may be improved.
  • Examples of the metal of the metal seed layer 200 are not particularly limited, and include copper, chromium, nickel, tin, gold, silver, platinum, cobalt, aluminum, molybdenum, tungsten, and the like.
  • this metal seed layer is not particularly limited, and may be, for example, in the range of about several nm to several hundred nm, preferably about 5 to 1000 nm.
  • the plating layer 300 is formed on the metal seed layer 200.
  • the plated layer 300 may be connected to the plated layer of another substrate through a hole to form a new circuit layer.
  • Examples of the metal of the plating layer 300 include copper, gold, silver, tin, nickel, and the like.
  • the thickness of the plating layer is not particularly limited, and may be about 1 to 50 ⁇ m, and preferably about 5 to 12 ⁇ m, and fine pattern implementation is suitable.
  • the printed circuit board includes a metal foil 40, an insulating layer 100, a metal seed layer 200, and a plating layer 300. It is not limited to this.
  • the insulating layer 100 is formed on one surface of the metal foil, and may be formed of any one of the insulating resin films shown in FIGS. 2 to 7.
  • the insulating layer 100 is formed by sequentially stacking the polyimide resin layer 20 and the insulating resin layer 10 on the metal foil 40. Formed (see FIG. 14).
  • One or more holes (hereinafter, referred to as 'first holes') 110 are formed in the insulating layer 100.
  • Roughness surface 100A formed on the surface of the insulating layer 100 and the inner wall surface of the first hole as described above by removing rubber particles by desmear treatment or by removing silica particles by desmear treatment or alkaline aqueous solution treatment. There is.
  • the rough surface 100A may be chemically and physically coupled to the metal seed layer formed on the surface of the insulating layer and the inner wall surface of the first hole, thereby improving adhesion characteristics.
  • the metal foil 40 may have a hole (hereinafter, referred to as a “second hole”) (not shown) corresponding to the position of the first hole.
  • a second hole a hole corresponding to the position of the first hole.
  • the metal seed layer and the plating layer are sequentially formed on the inner wall surface of the second hole.
  • the thickness sum of the plating layer 300 and the metal seed layer 200 is generally the same as the sum of the thickness of the metal foil 40 because the metal foil is used symmetrically when used as the outer layer and the inner layer.
  • the printed circuit board of the present invention can be manufactured by various methods using the above-described insulating resin film.
  • the manufacturing method may include forming one or more holes 110 in an insulating layer 100 formed by stacking one or more insulating resin films, as shown in FIG. 15; Removing the rubber particles (12) on the surface of the insulating layer and the inner wall of the hole by a desmear process to form a roughness surface (100A); Forming a metal seed layer (200) on the roughness surface (100A); And forming a plating layer 300 on the metal seed layer 200, but is not limited thereto.
  • each step may be performed in a continuous process by a roll-to-roll method.
  • each step may be performed in a continuous process by a roll-to-roll method.
  • each step may be performed in a continuous process by a roll-to-roll method.
  • the manufacturing method may include forming an insulating layer 100 by laminating one or more insulating resin films on the metal foil 40; Forming at least one first hole (110) in the insulating layer (100); Removing the silica particles (13) on the surface of the insulating layer and the inner wall of the first hole by a desmear treatment or an aqueous alkali solution to form a roughness surface (100A); Stacking a protective film layer 400 on an opposite surface of the metal foil 40 on which the insulating layer 100 is stacked; Forming a metal seed layer (200) on the roughness surface (100A); And forming a plating layer 300 on the metal seed layer 200, but is not limited thereto.
  • each step may be performed in a continuous process by a roll-to-roll method.
  • one or more holes 110 are formed in the insulating layer 100 formed by stacking one or more of the above-described insulating resin films (hereinafter, 'S100 step'). ).
  • the step S100 may be performed by a roll-to-roll method. Specifically, the step S100 may be performed by forming one or more holes in the insulating layer while unwinding the insulating layer wound on one roller and then rewinding the other roller.
  • a roll-to-roll method it can be carried out continuously so that yield improvement and economic benefit can be raised, and also a large-area substrate can be produced, which is preferable.
  • the hole 110 is formed in the insulating layer 100 by a mechanical processing method such as a drill or laser irradiation or by a chemical etching method. Among them, the hole is preferably formed by irradiating a laser.
  • the laser may be an excimer laser, UV laser and carbon dioxide (CO 2 ) laser.
  • At least one insulating resin film is laminated on the metal foil 40 to form the insulating layer 100, and then at least one hole ('first hole') 110 is formed in the insulating layer 100.
  • holes ('second hole') may be formed together on the metal foil portion corresponding to the position of the first hole to be formed.
  • the insulating layer material remaining in the metal foil can be removed.
  • the metal seed layer 200 and the plating layer 300 are respectively formed, the metal seed layer and the plating layer are sequentially formed on the inner wall surface of the second hole (not shown).
  • the surface of the insulating layer and the hole inner wall surface are treated with a desmear treatment or an aqueous alkali solution to form a roughness surface ('S200 step').
  • the step S200 may be performed by a roll-to-roll method. Specifically, after the one or more holes are formed in step S100, the surface of the insulating layer and the inner wall of the hole may be desmeared or alkali while releasing the roller wound insulating layer again. Aqueous treatment may be performed to form a rough surface, and then rewind to another roller.
  • the desmear process removes rubber particles present on the surface of the insulating layer and the hole inner wall surface by an oxidizing agent such as permanganate, dichromate, etc., and the rubber particles 12 on the surface of the insulating layer and the hole inner wall surface.
  • an oxidizing agent such as permanganate, dichromate, etc.
  • This desmear process proceeds in the order of swell, oxidizer and neutralization, as is known in the art, wherein the solution used may be used without particular limitation as long as it is known in the art.
  • Alkaline aqueous solution treatment is a process of removing the silica particle which exists in the surface of an insulating layer and the hole inner wall surface by alkaline aqueous solution, such as potassium hydroxide (KOH) aqueous solution, similarly to the desmear process, the surface of the insulating layer and the hole inner wall As the surface silica particles 13 are removed as shown in Figs. 17 (c) and 18 (c), a rough surface 100A having fine grooves formed on the surface of the insulating layer and the surface of the hole inner wall is formed. By 100A), the adhesive strength between the insulating layer and the plating layer can be improved.
  • alkaline aqueous solution such as potassium hydroxide (KOH) aqueous solution
  • the aqueous alkali solution is an aqueous solution containing a hydroxide of an alkali metal or an aqueous solution containing a hydroxide of an alkaline earth metal, and the like, for example, an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution, but are not limited thereto.
  • the insulation is formed.
  • the method may further include laminating the protective film layer 400 on the opposite surface of the metal foil 40 on which the layer 100 is laminated (see FIGS. 16D and 18D). By further laminating the protective film layer 400, the metal seed layer 200 and the plating layer 300 may be formed on only one surface.
  • the protective film layer 400 is formed after removing the plating layer.
  • the step of laminating the protective film layer may also be performed by a roll-to-roll method, wherein the opposite end surface of the metal foil on which the insulating layer is laminated is formed at the winding end of the laminate of the metal foil and the insulating layer and the winding end of the protective film layer.
  • the laminated body of the said metal foil and an insulating layer, and a protective film layer are wound together by a roll-to-roll system in the state which contacted the layer.
  • the protective film layer may be a peelable plastic film or the like known in the art, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate (PET) film, or the like, which is a kind of plastic.
  • a peelable plastic film or the like known in the art, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate (PET) film, or the like, which is a kind of plastic.
  • the metal seed layer 200 is formed on the surface of the insulating layer and the inner wall of the hole (step S300).
  • the metal seed layer 200 to be formed is formed by chemically and physically bonded to the rough surface formed in the step S200.
  • the step S300 may form a metal seed layer while winding the roller wound after the desmear treatment or the aqueous alkali solution in the step S200 in a roll-to-roll manner.
  • a relatively thin metal is formed by performing electroless plating or sputtering on the surface of the insulating layer and the inner wall of the hole.
  • the seed layer 200 is formed.
  • the metal seed layer 200 is to secure the adhesive strength to the insulating layer 100 in advance in order to raise the fine circuit pattern layer thereon.
  • the fine grooves present in the roughness surface of the insulating layer and the roughness surface of the inner wall of the hole are filled with a metal component to form an anchor of the metal seed layer, thereby not only chemically bonding the metal seed layer 200 to the insulating layer 100. It may also be physically coupled, so that the adhesive strength between the metal seed layer 200 and the insulating layer 100 may be improved.
  • the metal seed layer 200 may be formed by an electroless plating method or a metal sputtering method, but is not limited thereto.
  • the thickness of the metal seed layer is not particularly limited, and may be, for example, in the range of several nm to several hundred nm.
  • a plating layer 300 is formed on the metal seed layer 200 (S400). step').
  • the plated layer formed is connected to the plated layer of another substrate through holes when three or more printed circuit boards are formed by repeating the above-described processes, thereby forming a new circuit layer.
  • the step S400 may form a plating layer while winding the roller, which is wound together with the insulating layer and the metal seed layer (or the metal foil, the insulating layer, and the metal seed layer) in the roll-to-roll method in step S300.
  • the method of forming the plating layer 300 is not particularly limited, and examples thereof include an electrolytic plating method and an electroless plating method, and an electrolytic plating method is preferable.
  • a photoresist is laminated on the metal seed layer by a lithography process, an opening for forming a pattern is formed to form a fine circuit pattern, and then a fine circuit in the opening.
  • the plating layer for forming a pattern is formed by an electroplating method or the like. The unnecessary photoresist is then removed and the exposed metal seed layer is removed to form a circuit pattern.
  • Examples of the photoresist include a dry film, but are not limited thereto.
  • the thickness of the plating layer is not particularly limited, and may be about 1 to 50 ⁇ m, and preferably about 5 to 12 ⁇ m, and fine pattern implementation is suitable.
  • the thickness of the plating layer 300 and the thickness of the metal seed layer 200 are equal to the thickness of the metal foil 40 when the plating layer is formed. It is desirable to adjust as possible.
  • 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.
  • liquid polyimide resin (DIC UNIDIC-V800), 10 parts by weight of rubber (Nagase's TEISAN Rubber (SG-P3)) and 1 part by weight of Talc (Sip-95 by Nippon Talc) are insulated
  • a resin composition (viscosity: 1,100 cps) was prepared.
  • the insulating resin composition was applied to a release liner with a thickness of 4 ⁇ m, and then heated to 160 ° C. to prepare an insulating resin film having an insulating resin layer formed on the release liner.
  • a sweller (Atotech, Sweller-p, 40%), Oxidizer (The rubber was removed by desmearing in the order of 9% KMnO 4 , NaOH, 6%) and neutralization (H 2 SO 4, 9%).
  • electrolytic copper plating was performed to form a copper plating layer.
  • an etching process was performed to form a metal circuit pattern (100 mm ⁇ 10 mm).
  • An insulating resin film and a flexible printed circuit board were manufactured in the same manner as in Example 1, except that 20 parts by weight of the rubber particles used in Example 1-1 were used instead of 10 parts by weight.
  • An insulating resin film and a flexible printed circuit board were manufactured in the same manner as in Example 1, except that 30 parts by weight of the rubber particles used in Example 1-1 were used instead of 10 parts by weight.
  • Insulating resin composition (viscosity) by mixing 100 parts by weight of a liquid polyimide resin (UNICIC-V800 manufactured by DIC), 10 parts by weight of silica particles (SC-2050), and 1 part by weight of Talc (SG-95 manufactured by Nippon Talc) : 1000 cps) was prepared. Thereafter, the insulating resin composition was applied to a release liner with a thickness of 4 ⁇ m, and then heated to 160 ° C. to prepare an insulating resin film having an insulating resin layer formed on the release liner.
  • a liquid polyimide resin UNICIC-V800 manufactured by DIC
  • SC-2050 silica particles
  • Talc SG-95 manufactured by Nippon Talc
  • a sweller Atotech, Sweller-p, 40%
  • Oxidizer Silica was removed by desmearing in the order of 9% KMnO 4 , NaOH, 6%) and neutralization (H 2 SO 4, 9%).
  • electrolytic copper plating was performed to form a copper plating layer.
  • an etching process was performed to form a metal circuit pattern (100 mm ⁇ 10 mm).
  • An insulating resin film and a flexible printed circuit board were manufactured in the same manner as in Example 4, except that 20 parts by weight of the silica particles used in Example 4-1 were used instead of 10 parts by weight.
  • An insulating resin film and a flexible printed circuit board were manufactured in the same manner as in Example 4, except that 30 parts by weight of the silica particles used in Example 4-1 were used instead of 10 parts by weight.
  • a polyimide film (APICAL ® 12.5 NPI, Kaneka Co., Ltd., 12.5 ⁇ m thick) was used instead of the liquid polyimide resin used in Example 1-1, except that no rubber particles were used.
  • the flexible printed circuit board was prepared.
  • Ra value is an average value of the heights calculated over the entire measurement area. The absolute value of the height that changes in the measurement area is measured from the surface of the average line and then arithmetic averaged, in this case, the average roughness of 10 points. It is the value measured according to the calculation.
  • SEM scanning electron microscope
  • Lead heat resistance Desmear treatment of the insulating resin films prepared in Examples 1 to 6 and Comparative Example 1 to remove the rubber (or silica), followed by electrolytic copper plating, followed by copper plating layer After forming, it was cut to prepare a specimen (size: 5 cm ⁇ 5 cm), respectively. Thereafter, the specimen was placed in a lead bath at 288 ° C. and left for 1 minute, and then the separation between the insulating resin film and the copper foil layer and the contamination were observed visually. At this time, lead heat resistance was evaluated as follows.
  • peeling area between the plating layer and the insulating resin film is 10% or less
  • Drill Dust Specimens from which rubber particles (or silica particles) were removed by desmearing the insulating resin films (with the release liner removed) of Examples 1 to 6 and Comparative Example 1, respectively. Thereafter, each specimen was drilled using a mechanical drill [Hole Size: 0.15 mm, Pitch (Hole distance: 0.335 mm)], and then the drilled surface was observed for dust using an optical microscope. At this time, it evaluated as follows.
  • Examples 1 to 6 had a higher surface roughness value (Ra) than Comparative Example 1, which was also confirmed in the SEM photograph shown in FIG. In addition, Examples 1 to 6 had higher plating adhesion and high temperature adhesion than Comparative Example 1.
  • the printed circuit board manufactured using the insulating resin film according to the present invention was confirmed to have excellent room temperature / high temperature adhesiveness between the plating layer and the insulating layer, compared to the printed circuit board manufactured using the conventional general-purpose PI.
  • the insulating resin film is manufactured by changing the content of rubber to 3 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight and 40 parts by weight, respectively. Were prepared respectively. Thereafter, for each printed circuit board (Samples 1 to 5), as in Experiment 1, surface roughness (Ra), plating adhesion (P / S), high temperature adhesion (high temperature P / S), appearance, lead heat resistance, and chemical resistance And the drill dust were measured.
  • the printed circuit was carried out in the same manner as in Example 4 except that the insulating resin film was prepared by varying the content of silica particles by 3 parts, 10 parts, 20 parts, 30 parts, and 40 parts by weight, respectively. Each substrate was prepared. Then, the surface roughness (Ra), plating adhesion (P / S), high temperature adhesion (high temperature P / S), appearance, lead heat resistance, chemical resistance for each printed circuit board (samples 6 to 10) as in Experiment 1 And the drill dust were measured.
  • the content of the silica particles is more than 5 parts by weight, less than 40 parts by weight, it was found that normal temperature / high temperature adhesion between the insulating layer and the plating layer can be improved while maintaining excellent thermal and mechanical properties of the insulating resin film.

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

Abstract

La présente invention concerne un film isolant conçu pour améliorer la résistance d'adhésion à la couche métallisée dans une carte de circuit imprimé. L'invention concerne en outre une couche métallique mince et une carte de circuit imprimé comprenant ledit film isolant de résine, ainsi qu'un procédé de fabrication d'une carte de circuit imprimé mettant en œuvre ledit film isolant de résine.
PCT/KR2014/000311 2013-01-10 2014-01-10 Film isolant de résine, substrat comprenant une couche métallique mince, carte de circuit imprimé comprenant un film isolant de résine et procédé de fabrication de carte de circuit imprimé comprenant un film isolant de résine Ceased WO2014109593A1 (fr)

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PCT/KR2014/000311 Ceased WO2014109593A1 (fr) 2013-01-10 2014-01-10 Film isolant de résine, substrat comprenant une couche métallique mince, carte de circuit imprimé comprenant un film isolant de résine et procédé de fabrication de carte de circuit imprimé comprenant un film isolant de résine

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KR (1) KR20140090961A (fr)
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US10568212B2 (en) 2014-11-28 2020-02-18 Intel Corporation Manufacturing method for multi-layer printed circuit board
TWI688318B (zh) * 2014-11-28 2020-03-11 美商英特爾股份有限公司 多層印刷電路板的製造方法

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