WO2023219190A1 - Couche de libération composite pour feuille métallique fixée à un support et feuille métallique la comprenant - Google Patents

Couche de libération composite pour feuille métallique fixée à un support et feuille métallique la comprenant Download PDF

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Publication number
WO2023219190A1
WO2023219190A1 PCT/KR2022/006849 KR2022006849W WO2023219190A1 WO 2023219190 A1 WO2023219190 A1 WO 2023219190A1 KR 2022006849 W KR2022006849 W KR 2022006849W WO 2023219190 A1 WO2023219190 A1 WO 2023219190A1
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Prior art keywords
release layer
metal
carrier
metal foil
layer
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PCT/KR2022/006849
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English (en)
Korean (ko)
Inventor
전성욱
정보묵
김대근
양동민
강진석
박민영
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와이엠티 주식회사
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Publication of WO2023219190A1 publication Critical patent/WO2023219190A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to a composite release layer for metal foil attached to a carrier and a metal foil containing the same.
  • printed circuit boards can be manufactured by combining metal foil and an insulating resin substrate and then forming circuit wiring on the metal foil through an etching process.
  • a metal foil with high work convenience by securing high adhesion and release force between insulating resin substrates is required.
  • Patent Document 1 discloses that the adhesion between the copper foil and the resin layer is improved by forming particulate protrusions by subjecting the surface of the copper foil on the resin layer side to electrolytic treatment, blast treatment, or oxidation-reduction treatment.
  • metal foil is handled by combining a release layer and a carrier on one side.
  • the metal foil to which the release layer and the carrier are bonded must have heat resistance during the bonding process with the insulating resin substrate or the target substrate, and it is required that the carrier be easily peeled off through the release layer after bonding.
  • a technology has been proposed that applies organic components to the release layer or provides a separate layer between the release layer and the metal foil to increase heat resistance.
  • the present invention manufactures an organic-inorganic composite release layer by mixing a metal component with an organic release layer, and improves the disadvantage of staining when using the existing organic release layer.
  • the object is to provide a layer and a metal foil containing the same.
  • the present invention seeks to provide a composite release layer for metal foil with a carrier that can be applied to copper strike plating by using a metal-containing release layer and an organic-inorganic composite release layer, and a metal foil containing the same.
  • the present invention provides a release layer that allows the carrier to be smoothly removed from the carrier-attached metal foil, wherein the release layer includes a metal-containing release layer formed on the carrier; and an organic-inorganic release layer formed on the metal-containing release layer, wherein the organic-inorganic release layer includes a heterocyclic compound containing nitrogen; Amine-based compounds; and a composite release layer for metal foil with a carrier containing a transition metal compound of groups 3 to 8.
  • the heterocyclic compounds include benzotriazole, mercapto benzimidazole, mercapto benzotriazole, sodium mercapto benzotriazole, and 5-carboxybenzotriazole.
  • (5-Carboxybenzotriazole) 3-Amino-5-mercapto-1,2,4-triazole (3-Amino-5-mercapto-1,2,4-triazole), 3-mercapto-1,2, 4-Mercapto-1,2,4-triazole, Triazole-5-carboxylic acid, 1-methyl-3-mercapto-1,2,4-triazole (1-Methyl-3-mercapto-1,2,4-triazole) and 1-Phenyl-5-mercapto tetrazole (1-Phenyl-5-mercapto tetrazole). there is.
  • the amine-based compound is ethanolamine, 2-(methylamino)ethanol, 2-methoxyethylamine, 2-amino-1-propanol, alaninol, 2-ethoxyethaneamine, N- At least one selected from the group of ethyl-N-propylamine, tributylamine, 2-(dimethylamino)ethanol, N,N-dimethylbenzenamine, N,N-dibutylbutanamine, and N-ethylpropanamine It can be included.
  • the transition metal compound of groups 3 to 8 may be a metal compound containing chromium, molybdenum, tungsten, or titanium.
  • the transition metal compound is an oxide of chromium, molybdenum, tungsten, or titanium; Hydroxides of chromium, molybdenum, tungsten or titanium; Sulfates, nitrates, phosphates, hydrochlorides, fluorides or acetates of chromium, molybdenum, tungsten or titanium; Alternatively, it may include compounds derived from oxides of chromium, molybdenum, tungsten, or titanium.
  • the transition metal compounds of groups 3 to 8 include chromic acid, chromium (III) picolinate, potassium dichromate, chromium oxide, chromyl chloride, chromium sulfate, tungsten dioxide, tungsten trioxide, tungsten disulfide, It may contain tungsten trisulfide, tungsten dichloride, tungsten hexachloride, tungsten tetrachloride, ditungsten decachloride, tungsten trichloride, titanium tetrachloride, titanium disulfide, titanium halide, molybdenum oxide, molybdenum sulfide or molybdenum hexacarbonyl. there is.
  • the metal-containing release layer may include nickel and molybdenum.
  • the metal-containing release layer may include 50 to 80% by weight of Ni and 20 to 50% by weight of molybdenum.
  • the release layer may have a peel strength of 1 to 20 gf/cm when evaluated according to the IPC-TM-650 standard.
  • the metal-containing release layer may have a thickness of 0.01 to 0.2 ⁇ m, and the organic-inorganic release layer may have a thickness of 0.001 to 0.01 ⁇ m.
  • the present invention also provides a metal foil attached to a carrier including the composite release layer.
  • the metal foil attached to the carrier includes: a carrier; The composite release layer provided on the carrier; and a metal layer provided on the composite release layer, wherein the metal layer may include a metal foil including a plurality of protrusions.
  • the metal layer includes: a metal strike layer formed on the release layer; and a metal foil including a plurality of protrusions formed on the metal strike layer.
  • the metal strike layer may be formed under conditions of pH 8 to 11 using metal pyrophosphate.
  • the plurality of protrusions may have flat tops.
  • the composite release layer for metal foil attached to a carrier according to the present invention and the metal foil containing the same are manufactured by mixing metal components in an organic release layer to produce an organic-inorganic composite release layer, which improves the disadvantage that stains may occur when using the existing organic release layer. You can.
  • the composite release layer for metal foil attached to a carrier and the metal foil containing the same use a metal-containing release layer and an organic-inorganic composite release layer and can be applied to copper strike plating using a neutral plating solution.
  • Figure 1 shows a cross section of a conventional carrier-attached metal foil.
  • Figure 2 shows a cross section of a metal foil attached to a carrier according to an embodiment of the present invention.
  • Figure 3 shows a bonding structure of an organic-inorganic release layer according to an embodiment of the present invention.
  • Figure 4 shows the behavior of the organic and inorganic release layer when the release layer is released according to an embodiment of the present invention.
  • Figure 5 shows the phase equilibrium diagram of a chromium compound according to an embodiment of the present invention.
  • Figure 6 shows a phase equilibrium diagram of a transition metal compound according to an embodiment of the present invention, where (a) shows molybdenum, (b) shows titanium, and (c) shows tungsten.
  • Figure 7 shows a plurality of protrusions formed on a metal foil according to an embodiment of the present invention.
  • Figure 8 shows the appearance of protrusions having various shapes according to an embodiment of the present invention.
  • Figure 9 shows a photograph showing a protrusion with a flat top formed according to an embodiment of the present invention.
  • Figure 10 shows a photograph of metal foil after release of the carrier layer according to an embodiment of the present invention.
  • Figure 11 shows a photograph of metal foil after release of the carrier layer according to an embodiment of the present invention.
  • each process forming the method may occur differently from the specified order unless a specific order is clearly stated in the context. That is, each process may occur in the same order as specified, may be performed substantially simultaneously, or may be performed in the opposite order.
  • 'and/or' includes a combination of a plurality of listed items or any of a plurality of listed items.
  • 'A or B' may include 'A', 'B', or 'both A and B'.
  • the present invention relates to a release layer that allows the carrier to be smoothly removed from the carrier-attached metal foil, wherein the release layer includes a metal-containing release layer formed on the carrier; and an organic-inorganic release layer formed on the metal-containing release layer, wherein the organic-inorganic release layer includes a heterocyclic compound containing nitrogen; Amine-based compounds; and a composite release layer for metal foil with a carrier containing a transition metal compound of groups 3 to 8.
  • Figure 1 shows a carrier adhesive release layer including a conventional release layer.
  • the release peeling layer 250 and the release layer 240 of a metal component are used, so the metal component diffuses into the copper foil layer or the metal release layer is deposited on the surface of the copper foil during release.
  • the component of (240) is transferred, causing a defect in which the performance of the copper foil is deteriorated.
  • a technique is used to prevent diffusion and transfer of metal components by using an organic release layer 230 or forming an organic diffusion barrier layer on the surface of the metal release layer (FIG. 1(b)).
  • these organic components have the disadvantage of not being applicable to strike plating, which is widely used in forming metal foil, because they contain nitrogen.
  • Figure 2 shows the metal foil with a carrier of the present invention.
  • a metal-containing release layer is formed on the carrier layer, and an organic-inorganic release layer is formed between the metal-containing release layer and the metal foil to prevent metal diffusion and minimize stains or metal transfer during release.
  • a composite release layer for metal foil with a carrier attached is provided.
  • the release layer includes a metal-containing release layer formed on the carrier; And it may include an organic-inorganic release layer formed on the metal-containing release layer.
  • the metal-containing release layer 220 is a layer formed on the carrier 300 to facilitate release of the carrier, and may include nickel and molybdenum.
  • an organic/inorganic release layer 210 can be additionally used to lower the release force of the metal-containing release layer 220, which will be described later.
  • a nickel-molybdenum alloy plating layer may be formed by simultaneously plating nickel and molybdenum.
  • the carrier layer can be immersed in a plating solution to form the metal-containing release layer, and the plating solution for forming the metal-containing release layer is nickel sulfate (NiSO 4 ) and nickel molybdate (Ni 2 MoO 4 ) may be included as a source of nickel and molybdenum.
  • the mixing ratio of the nickel sulfate and the nickel molybdate may be 1:5 to 5:1 in molar ratio, preferably 1:2 to 2:1 and most preferably 1:1. If mixed outside the above range, the desired release force may not be achieved due to insufficient molybdenum or nickel content, or residue may be generated during release due to excessive release force.
  • the nickel sulfate and the nickel molybdate may each be included in the plating solution at a ratio of 0.1 to 0.5 M. If it is included in less than the above ratio, a release layer of the desired thickness cannot be formed, and if it exceeds the above range, the surface roughness of the release layer may increase due to excessive precipitation.
  • the nickel sulfate and the nickel molybdate are 50 to 80% by weight of Ni and 20% by weight of molybdenum in the metal-containing release layer. It may contain ⁇ 50% by weight. Also, in this case, the molar ratio of nickel and molybdenum may be about 1:1 to 4:1.
  • the surface roughness of the metal-containing release layer is lowered and plated to a uniform thickness, so that the desired release force can be obtained. However, if it is outside the above range, the desired release force cannot be obtained, or residue may be generated during release due to excessive release force. You can.
  • the plating solution may include citric acid or tartaric acid in addition to the nickel sulfate and nickel molybdate.
  • the citric acid or tartaric acid may be mixed in the plating solution at a ratio of 0.2 to 0.4 M. If the content is less than the above ratio, the desired plating may not be performed, and if it is more than the above range, the thickness of the plating layer may not be constant, and the surface roughness may increase undesirably.
  • the organic-inorganic release layer 210 may be formed.
  • the organic-inorganic release layer 210 is a layer that prevents the metal contained in the metal-containing release layer 220 from diffusing into the interior of the metal foil, which will be described later, or from being transferred to the surface of the metal foil during release, and is a heterocycle containing nitrogen. It may include compounds, amine compounds, and transition metal compounds of groups 3 to 8.
  • an organic and inorganic release layer can be formed by including a transition metal compound when forming the organic release layer, and through this, stains generated during release can be minimized.
  • the organic-inorganic release layer includes a heterocyclic compound containing nitrogen, an amine-based compound; and transition metal compounds of groups 3 to 8.
  • the heterocyclic compound containing nitrogen refers to a compound in which one or more atoms constituting the ring of a cyclic compound are replaced with an atom other than carbon. In the case of the present invention, the carbon atom of the ring is replaced with nitrogen. Heterocyclic compounds can be used.
  • the heterocyclic compound is a cyclic compound having two or more nitrogen atoms, more specifically, benzotriazole, mercapto benzimidazole, and mercapto benzotriazole.
  • 1-Methyl-3-mercapto-1,2,4-triazole and 1-phenyl-5-mercaptotetrazole (1 -Phenyl-5-mercapto tetrazole) may include one or more selected from the group consisting of
  • the heterocyclic compound may be used as a single component, but two or more types of heterocyclic compounds may be used in combination to facilitate release during peeling.
  • the mixing ratio of each heterocyclic compound may be 1 to 5: 5 to 1, and is preferably used in a 1:1 ratio, that is, equal amounts can be mixed. . If the heterocyclic compound is mixed in a ratio outside the above range, it is difficult to expect an effect from mixing.
  • the heterocyclic compound may be mixed and used in a plating solution at a ratio of 50 to 200 g/L during plating to form the organic-inorganic release layer. If the heterocyclic compound is mixed at a ratio of less than 50 g/L, the peeling strength of the organic-inorganic release layer may be lowered and the carrier may be separated at an undesirable point, and if the heterocyclic compound is mixed at a ratio exceeding 200 g/L, the amine to be described later Defects may occur during plating due to the presence of heterocyclic compounds that are not dissolved by the base compound.
  • the amine-based compound can be used as a solvent to dissolve the heterocyclic compound and at the same time react with a metal compound to be described later to secure an appropriate mold release force.
  • the amine-based compound refers to a compound in which at least one of the hydrogen atoms of ammonia is replaced with a hydrocarbon.
  • Examples of the primary amine alcohol-based compounds include ethanolamine, 2-(methylamino)ethanol, 2-methoxyethylamine, 2-amino-1-propanol, alaninol, 2-ethoxyethaneamine, N -One or more selected from the group of ethyl-N-propylamine, tributylamine, 2-(dimethylamino)ethanol, N,N-dimethylbenzenamine, N,N-dibutylbutanamine, and N-ethylpropanamine It may include, and most preferably, ethanolamine may be used.
  • the amine-based compound may be included in an amount of 5 to 20 g/L in the plating solution during plating to form the organic-inorganic release layer. If the amine compound is contained in an amount of less than 5 g/L, the heterocyclic compound may not dissolve smoothly, making it difficult to form a smooth organic-inorganic release layer, and if it is contained in a ratio exceeding 20 g/L, the heterocyclic compound may be difficult to form. The ratio of is relatively low, which may reduce the peel strength.
  • an organic release layer is possible even when using a mixture of the heterocyclic compound and the amine-based compound.
  • nitrogen content remains during release, causing stains in many cases. (see left combination in Figure 3).
  • the organic release layer since it is connected to the upper and lower parts of the release layer through bonds by nitrogen oxygen and hydrogen, it has a disadvantage in that residues may be generated during release due to its high release force.
  • an organic-inorganic release layer is manufactured by mixing transition metal compounds of groups 3 to 8, thereby minimizing defects caused by residues and controlling the release force.
  • the organic-inorganic release layer may exist between the metal foil and the metal-containing release layer formed on the top of the carrier.
  • the heterocyclic compound used as the organic component may be connected through a bond between the metal-containing release layer and the metal foil by nitrogen oxygen and hydrogen having a strong bonding force.
  • the transition metal compound included in the organic-inorganic release layer it may be dispersed on the surface of the metal-containing release layer and the surface of the metal foil to form a layer.
  • the transition metal compound layer formed on the surface of the metal-containing release layer and the transition metal compound layer formed on the surface of the metal foil may be bonded to each other using hydroxy groups (see bond on the right side of Figure 3), but this is hydrogen bonding. It is a type of weak covalent bond, and since only some of the transition metals are bonded, it can have weak bonding strength. That is, if the amount of the transition metal compound included in the organic-inorganic release layer increases, the bond between the transition metal compound layers increases, thereby forming an organic-inorganic release layer with weak release force, and if the amount of the transition metal compound decreases, the bond between the transition metal compound layers increases. As the bonds caused by the heterocyclic compound are increased, a release layer with strong release force can be formed.
  • the transition metal compounds of groups 3 to 8 may be used without limitation as long as they are compounds containing transition metals belonging to groups 3 to 8, but are preferably metal compounds containing chromium, molybdenum, tungsten or titanium. .
  • the transition metal compound may be an oxide of chromium, molybdenum, tungsten or titanium; Hydroxides of chromium, molybdenum, tungsten or titanium; Sulfates, nitrates, phosphates, hydrochlorides, fluorides or acetates of chromium, molybdenum, tungsten or titanium; Alternatively, it may include compounds derived from oxides of chromium, molybdenum, tungsten, or titanium.
  • the organic-inorganic release layer has different film formation conditions depending on the type of metal component included in the organic-inorganic release layer, so it is desirable to select and use it appropriately according to each process condition.
  • the hydrous chromium oxide film can be formed between pH 6 and 10 (see Figure 5), and a transition metal compound containing molybdenum can form the hydrous chromium oxide film at pH 3 to 7 (see Figure 6).
  • transition metal compounds containing titanium form a film at pH 2 to 8 ((b) in Figure 6)
  • transition metal compounds containing tungsten form a film at pH 2 to 4 ((c) in Figure 6). This is possible. Therefore, it is desirable to use a compound containing an appropriate metal according to each process condition.
  • the transition metal compound may include chromic acid, chromium (III) picolinate, potassium dichromate, chromium oxide, chromyl chloride, or chromium sulfate.
  • chromic acid it can be most commonly used as a compound produced by dissolving chromium oxide, an oxide of chromium, in water.
  • Chromium(III) picolinate is a chromium compound that is easily degraded and decomposed, and can be easily used to form a Cr-N film.
  • Potassium dichromate has excellent oxidizing power and is the most commonly used chromium compound.
  • Chromium trioxide is commonly used as a metal salt in chrome plating solutions, and chromyl chloride can react with hydrochloric acid to form chromium salt.
  • chromium(III) sulfate a chromium sulfide film can be formed on the surface of the metal-containing release layer.
  • various transition metal compounds can be used in the organic-inorganic release layer, and can be appropriately selected and used according to each process.
  • Transition metal compounds such as molybdenum sulfide or molybdenum hexacarbonyl can be used.
  • the transition metal compound may be included in an amount of 20 to 2000 ppm by weight in the plating solution during plating to form the organic-inorganic release layer. If the transition metal compound is included at less than 20ppm, the stain prevention and release force control effects of the transition metal compound may not appear, and if it is included at a rate exceeding 2000ppm, the release force will be weakened and the carrier will separate at an unwanted time. It can be.
  • the organic-inorganic release layer is preferably performed under conditions of pH 5-7, current density 5-7 ASD, and plating time 20-60 seconds. Within the above range, the organic/inorganic release layer can be formed normally, but if it is outside the above range, the transition metal compound may not be plated on the surface of the carrier layer or it may be difficult to control the release force.
  • the current efficiency may be 5 to 30%.
  • a large amount of hydrogen may be generated, but the organic/inorganic release layer can be formed uniformly.
  • the release layer may have a peel strength of 1 to 20 gf/cm when evaluated according to the IPC-TM-650 standard. If the peel strength of the release layer is less than 1 gf/cm, the carrier may be separated at an undesirable time, and if it exceeds 20 gf/cm, a residue may remain when the carrier is peeled using the release layer.
  • the metal-containing release layer may have a thickness of 0.01 to 0.2 ⁇ m, and the organic-inorganic release layer may have a thickness of 0.001 to 0.01 ⁇ m.
  • the composite release layer may have a smooth release force. However, if the thickness is less than the above range, the metal component of the carrier may diffuse toward the metal foil, and if the thickness exceeds the above range, after release Release layer components may remain in the metal foil.
  • the present invention also provides a metal foil attached to a carrier including the organic-inorganic release layer.
  • the release layer of the present invention can be composed of a composite release layer of a metal-containing release layer and an organic-inorganic release layer. Accordingly, compared to the existing metal foil attached to a carrier, the release layer can minimize the occurrence of stains during release. It can have the advantage of being able to form .
  • the metal foil attached to the carrier includes: a carrier; The composite release layer provided on the carrier; and a metal layer provided on the composite release layer, wherein the metal layer may include a metal foil including a plurality of protrusions.
  • the metal foil 100 includes a plurality of protrusions 10 with flat tops.
  • the protrusions 10 may refer to metal crystal particles protruding vertically upward from the surface of the metal foil 100.
  • the protrusion 10 may include a protruding portion 11 and a flat portion 12 (see FIGS. 2 and 7).
  • the protrusion 11 included in the protrusion 10 is a portion that protrudes from the surface of the metal foil 100 and may have a truncated cone shape or a polygonal pyramid shape. Specifically, as shown in FIG. 2, the protrusion 11 has a truncated cone shape with a flat surface (side surface) or a polygonal pyramid shape with an angulated surface, and as a result, it forms an anchor in close contact with the insulating resin substrate 400. ) The effect is increased, so that the metal foil 100 can be combined with the insulating resin substrate to have high adhesion. More specifically, the protrusion 11 may have one or more shapes selected from the group consisting of a pentagonal pyramid shape, a hexagonal pyramid shape, a heptagonal pyramid shape, and an octagonal pyramid shape among polygonal pyramid shapes.
  • a plurality of fine protrusions 11a may be formed on the protrusion 11 to increase adhesion to the insulating resin substrate by increasing the surface area. Due to these fine protrusions 11a, the protrusion 11 may have a surface roughness (Ra) of 0.05 to 0.3 ⁇ m, specifically 0.08 to 0.2 ⁇ m.
  • the surface roughness (Ra) of the protrusion 11 may be defined as the surface roughness (Ra) of the side surface of the protrusion 11 excluding the flat portion 12.
  • the ratio (b/a) of the base length (a) of the protrusion 11 to the height (b) of the protrusion 11 may be 0.4 to 1.5, specifically 0.6 to 1.2. As the ratio (b/a) is within the above range, it is possible to increase the adhesion between the metal foil 100 and the insulating resin substrate and minimize signal transmission loss during high-frequency signal transmission.
  • the flat portion 12 included in the protrusion 10 is a flat surface provided at the top of the protrusion 11.
  • the flat portion 12 may refer to the upper surface of the protrusion 11 having a truncated cone shape or a polygonal pyramid shape.
  • the present invention has a flat portion where the top (top) of the protrusion 10 is a flat surface.
  • the surface of the metal foil 100 exhibits relatively low illumination, thereby minimizing high-frequency signal transmission loss.
  • the flat portion 12 may have a circular, oval, or polygonal shape (see FIG. 8). Meanwhile, even if fine irregularities are formed on the surface, a case where the fine irregularities are densely formed to form a flat surface can be considered to be included in the category of the flat portion 12 of the present invention.
  • the ratio (c/a) of the base length (a) of the protrusion 11 to the length (c) of the flat portion 12 may be 0.1 to 0.7, specifically 0.2 to 0.6. As the ratio (c/a) is within the above range, it is possible to increase the adhesion between the metal foil 100 and the insulating resin substrate and minimize signal transmission loss during high-frequency signal transmission.
  • the length (c) of the flat part 12 may mean the longest length on the surface forming the flat part 12.
  • the number of such protrusions 10 is per unit area (1 ⁇ m 2 ) of the metal foil 100, considering the adhesion between the metal foil 100 and the insulating resin substrate, high-frequency signal transmission efficiency, and circuit wiring resolution of the metal foil 100. It may be 25 or less, specifically 5 to 20, and more specifically 7 to 15 (see FIG. 9).
  • the protrusions 10 may be formed by electroless plating.
  • the metal foil 100 according to the present invention is manufactured by electroless plating. After the metal seed foil is formed in the electroless plating process, crystal grains continue to grow on the metal seed foil, and a plurality of protrusions 10 are formed on the surface.
  • the metal foil 100 present in can be manufactured.
  • the present invention performs a separate roughening process because a plurality of protrusions 10, which are roughened surfaces, are naturally formed during the manufacturing process of the metal foil 100. The process can be omitted, thereby improving the manufacturing efficiency of the metal foil 100 or/and the printed circuit board.
  • the metal foil 100 is manufactured by electroless plating, it is possible to provide a metal foil 100 that is thinner and more porous than the metal foil manufactured by electrolytic plating.
  • the electroless plating solution used during the electroless plating to manufacture the metal foil 100 according to the present invention is not particularly limited, but may be an electroless plating solution containing a metal ion source and a nitrogen-containing compound.
  • the metal ion source may specifically be one or more copper ion sources selected from the group consisting of copper sulfate, copper chloride, copper nitrate, copper hydroxide, and copper sulfamate.
  • the concentration of this metal ion source may be 0.5 to 300 g/L, specifically 100 to 250 g/L, and more specifically 190 to 200 g/L.
  • the nitrogen-containing compound diffuses metal ions so that a plurality of protrusions 10 are formed on the surface of the metal seed foil formed by the metal ion source.
  • the nitrogen-containing compounds specifically include purine, adenine, guanine, hypoxanthine, xanthine, pyridazine, methylpiperidine, 1,2-di-(2-pyridyl)ethylene, 1,2-di-(pyridyl) ) Ethylene, 2,2'-dipyridylamine, 2,2'-bipyridyl, 2,2'-bipyrimidine, 6,6'-dimethyl-2,2'-dipyridyl, di-2 -It may be one or more selected from the group consisting of pyryl ketone, N,N,N',N'-tetraethylenediamine, 1,8-naphthyridine, 1,6-naphthyridine, and terpyridine.
  • the electroless plating solution may further include one or more additives selected from the group consisting of a chelating agent, a pH adjuster, and a reducing agent.
  • the chelating agent specifically includes tartaric acid, citric acid, acetic acid, malic acid, malonic acid, ascorbic acid, oxalic acid, lactic acid, succinic acid, potassium sodium tartrate, dipotassium tartrate, hydantoin, 1-methylhydantoin, 1,3-dimethyl.
  • concentration of this chelating agent may be 0.5 to 600 g/L, specifically 300 to 450 g/L, and more specifically 400 to 430 g/L.
  • the pH adjuster may specifically be one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide. This pH adjuster may be included in the electroless plating solution so that the pH of the electroless plating solution is adjusted to 8 or more, specifically 10 to 14, and more specifically 11 to 13.5.
  • the reducing agent may be one or more selected from the group consisting of formaldehyde, sodium hypophosphite, sodium hydroxymethane sulfinate, glyoxylic acid, boron hydride, and dimethylamine borane.
  • the concentration of this reducing agent may be 1 to 20 g/L, specifically 5 to 20 g/L.
  • Plating conditions for manufacturing the metal foil 100 by electroless plating with the electroless plating solution can be appropriately adjusted depending on the thickness of the metal foil 100.
  • the electroless plating temperature may be 20 to 60°C, specifically 25 to 40°C
  • the electroless plating time may be 2 to 30 minutes, specifically 5 to 20 minutes.
  • the thickness of the metal foil 100 of the present invention manufactured by electroless plating may be 5 ⁇ m or less, specifically 0.1 to 1 ⁇ m.
  • the components that make up the metal foil 100 of the present invention are not particularly limited as long as they are known metals that can form the circuit layer of a printed circuit board, and specifically, they are selected from the group consisting of copper, silver, gold, nickel, and aluminum. There may be more than one type.
  • the carrier 300 included in the metal foil attached to the carrier according to the present invention prevents the metal layer from being deformed during movement or use of the metal attached to the carrier, and includes metals such as copper, aluminum, etc.; Alternatively, it may be made of polymers such as polyethylene terephthalate (PET), polyphenylene sulfide (PPS), Teflon, etc.
  • the thickness of this carrier may specifically be 10 to 50 ⁇ m.
  • the metal foil attached to a carrier according to the present invention may further include a rust prevention layer provided on the metal layer to protect the metal layer.
  • the rust prevention layer may include zinc, chromium, etc.
  • the metal layer may include: a metal strike layer formed on the release layer; And it may include a metal foil including a plurality of protrusions formed on the metal strike layer.
  • the metal layer may largely be composed of a metal strike layer formed on the release layer and a metal foil on which the plurality of protrusions are formed.
  • the metal strike layer is formed on the release layer and serves as a base for forming the metal foil, and may be formed using a strike plating process.
  • the metal strike layer 110 can be formed on the release layer to facilitate the formation of the metal foil (see Figure 2).
  • the metal strike layer 110 may be formed by a strike plating process, which refers to a process in which plating is performed for a short time under a high current density to increase the adhesion of plating with low adhesion.
  • the main plating process can be performed after the strike plating process, and in the case of the present invention, the metal foil can be formed using the electroless plating process as discussed above.
  • the metal strike layer is formed under conditions of pH 8 to 11 using metal pyrophosphate.
  • the metal contained in the organic-inorganic release layer may be oxidized by the acid, resulting in many stains.
  • the surface of the organic-inorganic release layer is neutral, it may become worse if acid electroplating is performed. Therefore, in the case of the present invention, it is preferable to perform the metal strike plating using a neutral plating solution.
  • the metal strike plating uses metal pyrophosphate as a metal source and can be performed at a current density of 2 to 6 ASD and a temperature of 50 to 60 ° C.
  • sulfate which is used as a metal source in existing plating solutions, can form an acidic plating solution, so in the case of the present invention, it is preferable to use metal pyrophosphate as a metal source.
  • the metal layer formed by strike plating may be a copper or aluminum layer. Therefore, it is preferable that the metal pyrophosphate is copper pyrophosphate or aluminum pyrophosphate.
  • the metal pyrophosphate may be included in the plating solution for the strike plating in an amount of 80 to 110 g/L, preferably 90 g/L. If the metal pyrophosphate is included at less than 80 g/L, it may be difficult to form the metal strike layer, and if it is added at a rate exceeding 110 g/L, the surface roughness of the metal strike layer may increase and defects may occur. .
  • potassium pyrophosphate may be added to form a buffer solution separately from the metal pyrophosphate.
  • This potassium pyrophosphate can maintain the pH of the plating solution appropriately by forming a buffer solution, thereby allowing the strike plating to be performed under neutral conditions.
  • the potassium pyrophosphate is preferably mixed in the plating solution for strike plating at a ratio of 250 to 400 g/L, preferably 290 to 370 g/L, and most preferably 340 g/L. If the potassium pyrophosphate is contained in less than 250 g/L, it may be difficult to maintain pH during strike plating, and if it is contained in a ratio exceeding 400 g/L, potassium may precipitate and cause defects during plating.
  • the strike plating is preferably performed under a current density of 2 to 6 ASD, preferably 3 to 5 ASD, and most preferably 4 ASD. If the current density is less than 2ASD, strike plating may not be performed, resulting in defective plating having a nodule shape. If the current density is more than 6ASD, the roughness may increase on the surface of the strike plating layer, creating a dark red matte surface. In addition, within the above current density range, the current efficiency may be more than 80%, but if it exceeds 6ASD, the current efficiency may rapidly decrease to less than 35%.
  • the strike plating is preferably performed under pH 8.0 to 11.0, preferably pH 8.7 conditions. If the strike plating is performed below pH 8.0, stains may occur on the surface in contact with the release layer as seen above, and if pH exceeds 11.0, the surface shape may have a nodule or spherical shape and defects may occur.
  • the strike plating may be performed at a temperature of 50 to 60°C, preferably 55°C. If the plating temperature is less than 50°C, current efficiency may be reduced, and if it exceeds 60°C, the roughness of the strike layer surface may increase.
  • the metal foil with a carrier according to the present invention may further include an antioxidant layer provided between the release layer and the metal layer.
  • the antioxidant layer may include nickel, phosphorus, etc.
  • the present invention provides a printed circuit board manufactured using the above-described metal foil.
  • the printed circuit board according to the present invention includes a metal circuit layer and an insulating resin layer 400, and the metal circuit layer is derived from the metal foil described above, which will be described as follows.
  • the metal circuit layer included in the printed circuit board according to the present invention is a layer on which circuit wiring is formed. This metal circuit layer is obtained through the process of forming circuit wiring on the above-described metal foil.
  • the present invention can provide a fine and high-resolution printed circuit board.
  • the printed circuit board according to the present invention is manufactured by performing an etching process on a laminate combining the insulating resin base and the above-described metal foil to form circuit wiring in the metal foil, and the metal foil has high adhesion to the insulating resin base. Although they are combined, their thickness is relatively thin, making it possible to form fine, high-resolution circuit wiring in metal foil.
  • the present invention can provide a printed circuit board that exhibits high adhesion between circuit wiring and an insulating resin substrate.
  • the method of forming the circuit wiring is not particularly limited and includes subtractive process, additive process, full additive process, semi additive process, Alternatively, it may be a modified semi additive process.
  • the insulating resin layer 400 included in the printed circuit board according to the present invention is an insulating layer provided on a metal circuit layer.
  • This insulating resin layer 400 may be made of a commonly known insulating resin substrate.
  • the insulating resin layer may be made of a resin substrate (eg, prepreg) having a structure in which inorganic fibers or organic fibers are impregnated with a commonly known resin.
  • the printed circuit board according to the present invention can be manufactured using an insulating resin base material, or can also be manufactured using a coreless method excluding the insulating resin base material.
  • the coreless method may not be particularly limited as long as it is a commonly known method.
  • a carrier foil made of copper foil (Cu foil) with a thickness of about 18 ⁇ m was immersed in 5% by weight sulfuric acid, pickled, and then washed with pure water.
  • the treated carrier foil was immersed in a plating solution containing nickel sulfate (NiSO 4 ), sodium molybdate (Na 2 MoO 4 ), and citric acid (Citrate), and then plating was performed.
  • NiSO 4 nickel sulfate
  • Na 2 MoO 4 sodium molybdate
  • citric acid citric acid
  • Example 1 0.3 0.05 0.3 6 6 40
  • Example 2 0.3 0.1 0.3 6 6 40
  • Example 3 0.3 0.3 0.3 6 6 40
  • Example 4 0.3 0.5 0.3 6 6 40
  • Example 5 0.3 0.8 0.3 6 6 40
  • Example 6 0.05 0.3 0.3 6 6 40
  • Example 7 0.1 0.3 0.3 6 6 40
  • Example 8 0.5 0.3 0.3 6 6 40
  • Example 9 0.8 0.3 0.3 6 6 40
  • Example 10 0.3 0.3 0.2 6 6 40
  • Example 11 0.3 0.3 0.4 6 6 40
  • Example 12 0.3 0.3 0.3 6 4 40
  • Example 14 0.3 0.3 0.3 6 4 40
  • Example 15 0.3 0.3 0.3 6 8 40
  • Example 16 0.3 0.3 0.3 6 10 10
  • Example 17 0.3 0.3 6 6 20
  • Example 18 0.3 0.3 0.3 6 6 60
  • Example 19 0.3 0.3 0.3 6 6 70
  • a metal-containing release layer was formed by changing the contents of nickel sulfate, sodium molybdate, and citric acid and each process condition.
  • the formation of the metal-containing release layer was not smooth under pH conditions below 4 and above 8, and that a large amount of hydrogen gas was generated when a current density of 8ASD was used. Although the amount of hydrogen generated was reduced under the condition of a current density of 4ASD, the plating rate was significantly reduced and an uneven metal-containing mold layer was formed.
  • Example 3 As a result, it was confirmed that the conditions of Example 3 were the most suitable conditions for forming the metal-containing release layer, and in the examples to be described later, the metal-containing release layer manufactured by the method of Example 3 was used.
  • an organic-inorganic release layer on top of the carrier + metal-containing release layer prepared in Example 3, it was immersed in a solution for forming an organic-inorganic release layer. At this time, the optimal organic-inorganic release layer was selected by varying the composition of the solution for forming the organic-inorganic release layer.
  • transition metal compound used in the organic-inorganic release layer was selected.
  • the transition metal compounds (ppm) shown in Table 2 below were added to a solution containing CBTA (5-carboxybenzotriazole, 100 g/L) and ethanolamine (10 g/L), and then immersed for 40 seconds at pH 9 and a temperature of 30°C. Thus, an organic-inorganic release layer was formed.
  • the copper strike plating was performed under the plating conditions shown in Table 3 below.
  • the prepared laminate was placed in an electroless plating bath and electroless plated to form a metal foil (copper foil) with a thickness of 1 ⁇ m on the release layer.
  • metal ion source CuSO 4 5H 2 O
  • nitrogen-containing compound Guanine
  • chelating agent potassium sodium tartrate
  • pH adjuster An electroless plating solution containing (NaOH) and a reducing agent (28% formaldehyde) was used, and electroless plating was performed at 30°C for 10 minutes.
  • the formed metal foil (including a single release layer)/Kraft paper/SUS plate was laminated in that order and pressed at 3.5 MPa pressure for 100 minutes at 200°C under vacuum to prepare a laminate.
  • the peel strength between the copper foil carrier foil (including a single release layer) and the ultra-thin layer was measured according to the IPC-TM-650 standard (BMSP-90P Peel tester, Test speed). : 50 mm/min, Test speed: 90°).
  • Example 22 which is judged to be the optimal condition, has an appropriate peel strength and does not cause staining (Figure 10 (a)), but when 5 ppm of the transition metal compound is used, the It was found that the mold release force control effect was poor, resulting in high mold release force, and it was also confirmed that the nitrogen component of CBTA used as a heterocyclic compound remained, causing stains after desmear ( Figure 10(b)). In addition, when the chromic acid exceeded 2000 ppm (Example 24), it was confirmed that the release force rapidly decreased due to excessive transition metal compounds.
  • Examples 25, 26, and 27 using transition metals other than chromium were found to have appropriate release force, and Examples 28 and 29 using other compounds of chromium also showed appropriate release force. It was confirmed that However, when metal compounds other than transition metal compounds of groups 3 to 8 are used, the release force becomes very weak and stains due to metal components occur (Example 30, Figure 10 (c)). There were cases where it was glued without being molded (Example 31), making it impossible to use.
  • Example 22 instead of the combination of 5-carboxybenzotriazole (100 g/L) and ethanolamine (10 g/L), a heterocyclic compound and an amine compound were added in combination at the ratios shown in Table 5 below, and the current density and plating The effect was measured by changing the time.
  • CBTA 5-carboxybenzotriazole
  • MT 3-mercapto-1,2,4-triazole
  • EA ethanolamine
  • AP 2-amino-1-propanol
  • Plating solution composition (g/L) CBTA MT EA AP
  • Example 32 50 - 10 - Example 33 100 - 10 - Example 34 200 - 10 - Example 35 - 100 10 - Example 36 100 - 5 - Example 37 100 - 10 - Example 38 100 - 20 - Example 39 100 - - 10
  • a laminate was manufactured and tested in the same manner as in Example 22, except that the conditions of Examples 32 to 45 were used.
  • Example 33 which is the optimal condition for the present invention, has appropriate peel strength and does not cause staining (Figure 11 (a)), but as the content of CTBA, a heterocyclic compound, increases, the peel strength decreases. It was confirmed that was rising. In addition, at 200 g/L of this heterocyclic compound, some staining occurred after desmearing, and therefore, it was confirmed that staining occurred at concentrations above this level. Additionally, when 50 g/L was used (Example 32), the content of the heterocyclic compound was reduced, confirming that the metal component of the metal-containing release layer was transferred to the strike copper layer (FIG. 11(b)).
  • Example 35 using a different type of heterocyclic compound, results similar to those of the present invention were seen.
  • Example 39 using AP showed similar results.

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Abstract

La présente invention concerne une couche de libération composite pour une feuille métallique fixée à un support et une feuille métallique la comprenant. La présente invention concerne une couche de libération composite pour une feuille métallique fixée à un support, la couche de libération permettant le retrait régulier d'un support de la feuille métallique fixée à un support, la couche de libération comprenant : une couche de libération contenant du métal formée sur le support ; et une couche de libération organique et inorganique formée sur la couche de libération contenant du métal, la couche de libération organique et inorganique contenant : un composé hétérocyclique contenant de l'azote ; un composé à base d'amine ; et un composé de métal de transition des groupes 3 à 8 du tableau périodique.
PCT/KR2022/006849 2022-05-09 2022-05-13 Couche de libération composite pour feuille métallique fixée à un support et feuille métallique la comprenant WO2023219190A1 (fr)

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JP2001215736A (ja) * 2000-02-04 2001-08-10 Jsr Corp フォトレジスト用剥離液組成物、剥離方法及び回路基板
KR101460553B1 (ko) * 2013-08-27 2014-11-12 도레이첨단소재 주식회사 가교밀도가 다른 이형층이 적층된 이형 필름
KR20160111985A (ko) * 2014-05-07 2016-09-27 미쓰이금속광업주식회사 캐리어 부착 구리박, 캐리어 부착 구리박의 제조 방법, 캐리어 부착 구리박을 사용하여 얻어지는 동장 적층판 및 프린트 배선판
KR20180090207A (ko) * 2017-02-02 2018-08-10 장 춘 페트로케미컬 컴퍼니 리미티드 복합의 얇은 전착 동박 및 캐리어
JP2021035755A (ja) * 2019-08-26 2021-03-04 東洋鋼鈑株式会社 キャリア層付き金属積層基材及びその製造方法、金属積層基材及びその製造方法、並びにプリント配線板

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Publication number Priority date Publication date Assignee Title
KR100869477B1 (ko) 2004-04-26 2008-11-21 주식회사 코오롱 이중 이형층을 가지는 스템핑 포일

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001215736A (ja) * 2000-02-04 2001-08-10 Jsr Corp フォトレジスト用剥離液組成物、剥離方法及び回路基板
KR101460553B1 (ko) * 2013-08-27 2014-11-12 도레이첨단소재 주식회사 가교밀도가 다른 이형층이 적층된 이형 필름
KR20160111985A (ko) * 2014-05-07 2016-09-27 미쓰이금속광업주식회사 캐리어 부착 구리박, 캐리어 부착 구리박의 제조 방법, 캐리어 부착 구리박을 사용하여 얻어지는 동장 적층판 및 프린트 배선판
KR20180090207A (ko) * 2017-02-02 2018-08-10 장 춘 페트로케미컬 컴퍼니 리미티드 복합의 얇은 전착 동박 및 캐리어
JP2021035755A (ja) * 2019-08-26 2021-03-04 東洋鋼鈑株式会社 キャリア層付き金属積層基材及びその製造方法、金属積層基材及びその製造方法、並びにプリント配線板

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