KR20220093621A - Flexible copper foil film and manufactruing method thereof - Google Patents

Abstract

The present invention relates to manufacturing of a conductive metal layer or fine metal pattern that can be used in an electrode system, an optical sensor and a conductive film of various electronic devices, a printed circuit and a semiconductor packaging substrate. The present invention relates to a flexible copper foil stacked film and furthermore, manufacturing of a fine metal pattern, wherein the flexible copper foil stacked film with high peel strength properties allows one side or both sides of an arbitrary substrate to be coated with a thin film functional undercoat and a primer by a wet process, and includes at least one metal selected from iron, cobalt, nickel, copper, silver, gold, aluminum, and tin or an alloy thereof on the top of the primer.

Description

Flexible copper foil film and its manufacturing method

The present invention relates to a functional undercoat and primer of a thin film, a flexible metal foil laminated film having high peel strength characteristics using the same, and a fine metal pattern manufacturing.

As the needs for light, thin, compact, and high-performance electronic devices and systems increase, various material technologies and electrode wiring technologies are required to implement them. For example, as a technology for implementing a metal circuit pattern in the case of manufacturing a sensor, semiconductor packaging substrate, and printed circuit board, a copper film laminated by an adhesive on a heat-resistant substrate or a thin copper film physically deposited A method of manufacturing a metal circuit pattern by forming a circuit pattern of a certain shape using a conventional photolithography process and etching copper is generally used. Such a traditional metal circuit pattern formation technique also has an inherent environmental pollution problem due to the complex and expensive facility investment and the generation of corrosive etching solutions. At the same time, additional investment in expensive and precise equipment is required along with expensive materials to implement a microcircuit pattern.

On the other hand, for fine wiring, a method of forming a surface roughness on the surface of a substrate through a desmear process and forming a conductor layer on the insulating layer on which the surface roughness is formed is also known. At this time, in the case of the SAP method of forming a conductor layer by plating after roughening the surface of the insulating layer with a desmear solution, if the surface roughness of the insulating layer is increased, the adhesion strength between the insulating layer and the chemical plating layer is increased However, there is a problem in that fine wiring becomes difficult. In addition, if the surface roughness is lowered for fine wiring, there is a problem in that the adhesive strength is lowered.

Therefore, there is a trade-off relationship between surface roughness and adhesive strength, and there is a need for a method to secure the adhesive strength between the substrate and the conductive layer while maintaining the miniaturization of the surface roughness and to implement fine wiring.

Korean Patent Publication No. 10-2011-0083448 (published on July 20, 2011)

Accordingly, the present invention pays attention to the problems found in the above literature, and applies a catalytically active layer capable of electroless plating on a target substrate by a low-cost wet thin film coating process, planarizes surface defects, and electroless plating method on the top thereof By forming a thin metal layer using In addition, an object of the present invention is to provide a flexible metal foil film having excellent pattern precision by applying a photolithography method, which is an existing process, in manufacturing a narrow tooth pattern, which is a subsequent process.

In order to achieve the above object, a catalyst active layer obtained by preparing a catalyst active material with a combination selected from an organic binder, a metal ion organic complex, an acid catalyst or a photoacid generator, a crosslinking agent, an organic solvent and a filler, and applying it on a substrate That the surface roughness of this base material can be refined|miniaturized. The present invention was completed by discovering that the upper part had excellent plating property by the electroless plating method and excellent adhesion between the metal plating film and the substrate to be plated. Furthermore, it was found that, in the case of manufacturing a narrow tooth pattern of a plating layer by a photolithography method, it is possible to manufacture a metal pattern having excellent pattern precision of 10 μm or less in line width.

The catalytically active layer is characterized in that it is formed by a blend having a composition selected from at least three selected from an organic binder, a metal ion organic complex, an acid catalyst or a photoacid generator, a filler, a crosslinking agent, and an organic solvent.

Alternatively, the catalytically active layer is characterized in that it is prepared by a formulation composed of a photopolymerizable binder, a metal ion organic complex, a filler, a photoinitiator, and an organic solvent.

The catalytically active layer has a thickness of 2 nm to 20 um, preferably 50 nm to 10 um, more preferably 500 nm to 2 um.

The narrow tooth pattern is manufactured by a photolithography method.

By the present invention, physical vapor deposition of prior patents is excluded, surface defects of the substrate can be planarized by the catalytically active layer based on the wet coating technique, excellent adhesion strength between the substrate and the plated metal layer, and the effect of realizing a low-cost fine metal pattern can indicate

1 is a simple cross-sectional illustration of a flexible metal foil (eg, copper foil) film having a metal layer on one or both sides of a polyimide.
2 is an illustration of a fine metal pattern manufacturing process by a modified semi-additive process (MSAP) method on the manufactured flexible metal foil film.
3 is a TEM image of silver nano-catalyst particles formed in a matrix after hard baking.
4 is an optical micrograph of a patterned copper layer on polyimide.
5 is an SEM photograph and XRD data of a copper layer patterned on polyimide.

Hereinafter, the present invention will be described in detail.

the present invention A catalytically active layer is coated on one or both surfaces of a substrate by a wet process, and on the upper part of the substrate, at least one metal selected from iron, cobalt, nickel, copper, silver, gold, aluminum, tin, or an alloy thereof with high peel strength It relates to a flexible metal foil film having properties and a narrow tooth pattern manufacturing thereof by a photolithography method.

The substrate may be glass, ceramic, three-dimensional plastic molded body, various plastics and films, etc. generally used in this technical field. More specifically, plastics and films have a glass transition temperature of 80 ^o C to 400 ^o C has a range of values. For example, polyethylene (PE) series, high fluorine resin series, polyolefin (PO) series, polyimide (PI) series, polysilicon series, polyurethane (PU) series, polyphenylsulfonyl (PPS) series, Liquid crystal polymer (LCP) series, epoxy series, polycarbonate (PC) series, cellulose series, polyvinyl chloride (PVC) series, phenolic resin series, melamine series, polyamide (PA) series, etc. can be used, More preferably, it is characterized in that it is selected from polyimide, polyphenylsulfonyl series, and liquid crystal polymer series, but is not limited thereto.

The catalytically active layer is characterized in that it is formed by a blend having a composition selected from at least three selected from an organic binder, a metal ion organic complex, an acid catalyst or a photoacid generator, a filler, a crosslinking agent, and an organic solvent.

Alternatively, the catalytically active layer is characterized in that it is prepared by a formulation composed of a photopolymerizable binder, a metal ion organic complex, a filler, a photoinitiator, and an organic solvent.

In the present invention, the organic binder must secure excellent developability in heat resistance, chemical resistance, adhesive strength improvement, and fine pattern production. Although not particularly limited, it includes carboxyl group monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, isoprenesulfonic acid, styrenesulfonic acid and 5-norbornene-2-carboxylic acid. copolymer resin, N-ethylmaleimide, N-propylmaleimide, N-methoxycarbonylmaleimide, N-furfurylmaleimide, N-cyclohexylmaleimide, N-butylmaleimide, 2, 5-dioxo-3-pyrroline-1-carboxamide, 3,4-dichloromethyl-pyrrole-2,5-dione, N-benzylmaleimide, N-phenylmaleimide, 3-methyl-N -phenylmaleimide, N-(ortho-toyl)-N-phenylmaleimide, N-(4-fluorophenyl)maleimide, N-(2,6-xylyl)maleimide; 3-Chloro-1-phenyl-pyrrole-2,5-dione, N-(2-chlorophenyl)-maleimide, N-(1-naphthalyl)-maleimide, 1-(2-trifluoromethyl- Copolymer resins prepared including maleimide monomers such as phenyl)-pyrrole-2,5-dione, alkylated melamine resins, phenol resins, urea resins, urethane-based resins, polypyrrolidinone, polyvinylphenol , polyvinyl alcohol, polystyrene, polymetamethyl acetate, polyvinyl acetate, polyamic acid, soluble polyimide, etc. may be used.

In particular, preferably, polyvinylphenol such as poly(4-vinylphenol) or an alkylated melamine resin such as poly(4-vinylphenol) may be used alone or in combination for the purpose of improving insulation, heat resistance and chemical resistance of the organic layer. Alkylated melamine resins that can be used are selected from melamine resins, or co-condensates, in which the N position is substituted with a methylol group and/or an alkoxymethyl group, and specific examples of such alkylated melamine resins include, but are not limited to, trimethylolmelaminetrimethylether , tetramethylolmelamine trimethyl ether, pentamethylol melamine trimethyl ether, hexamethylol melamine trimethyl ether, tetramethylol melamine tetramethyl ether, hexamethylol melamine tetramethyl ether, pentamethylol melamine tetramethyl ether, hexamethylol melamine tetramethyl ether, pentamethylol melamine pentamethyl ether, hexamethylol melamine pentamethyl ether, 2,4,6-{N,N-bis(methoxymethyl)amino}-1,3,5-triazine, etc. Alkoxymethylmelamines, such as a methoxymethylmelamine and the ethoxymethylmelamine corresponding to these, and a butoxymethylmelamine, are mentioned. Furthermore, it may have heterogeneous alkoxymethyl groups, such as a methoxymethyl group, an ethoxymethyl group, and a butoxymethyl group, in the same melamine nucleus. Moreover, it may be what was multimerized by a methylene bond, a dimethylene ether bond, etc. As the alkylated melamine resin, one having at least 3 or more, preferably 4 to 6 alkoxymethyl groups per melamine nucleus is usually used, and hexakismethoxymethylmelamine is particularly preferred. These are not necessarily a single compound, and may be a mixture of two or more types.

In the present invention, the photopolymerizable binder is not particularly limited, but for example, a polyfunctional monomer containing an ethylenically unsaturated bond, which is not limited thereto, but ethylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene group Polyethylene glycol diacrylate having a number of 2 to 14, or polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Acrylate, pentaerythritol tetramethacrylate, propylene glycol diacrylate having 2 to 14 propylene groups, or propylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol a compound obtained by esterifying a polyhydric alcohol such as hexaacrylate and dipentaerythritol hexamethacrylate with α,β unsaturated carboxylic acid; a compound obtained by adding acrylic acid or methacrylic acid to a compound containing a glycidyl group, such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; Compounds having hydroxyl groups or ethylenically unsaturated bonds, such as phthalic acid esters of β hydroxyethyl acrylate or β hydroxyethyl methacrylate, toluene diisocyanate adducts of β hydroxyethyl acrylate or β hydroxyethyl methacrylate, and many an ester compound with a carboxylic acid having a carboxy group of, or an adduct of a compound having a hydroxyl group or an ethylenically unsaturated bond and multi-isocyanate. The ethylenically unsaturated bond-containing polyfunctional monomer may be used alone or as a mixture of two or more types. The ethylenically unsaturated bond-containing polyfunctional monomer preferably has 3 or more functional groups having an ethylenically unsaturated bond in view of the shape of a fine pattern and chemical resistance adhesion properties during electroless plating. In addition to this, a monomer having an aziridine structure having a polyfunctional group, a monomer capable of crosslinking by a condensation reaction, and the like may be mentioned, but the present invention is not limited thereto.

In the present invention, the type of crosslinking agent is not particularly limited, but as a compound having a molecular weight within 50 to 1,000, a compound having a polyfunctional azide and a polyfunctional aziridine group, a substituted or unsubstituted aliphatic diamine, a substituted or Unsubstituted alicyclic diamine, substituted or unsubstituted alkylated melamine resin having a molecular weight of 300 to 100,000, unsubstituted aliphatic diol, substituted or unsubstituted alicyclic diol or hydroxy, amide, thiol as a reactive group for crosslinking in the molecular structure , may be selected from copolymers and polymer resins containing at least one imidazole, triazole, and the like.

The polyfunctional azide compound is not particularly limited, and generally includes, but is not limited to, a hydrophilic organic azido group, a hydrophobic organic azido group (including an amphiphilic organic azido group), a diazido organic crosslinking group, and an azide-substituted aromatic derivative. It includes any structure illustrated in Formulas 1 to 6. Examples of suitable azide substituted organic compounds include azide substituted polyoxyalkylenes, azide substituted organic amines (and ammonium salts thereof), azide substituted organic amides, azide substituted organic imines, azide substituted carboxylic acids, azides substituted carbonyl compounds (eg, ketones, carboxylic acids, carboxylate salts or esters), azide substituted alkyl polyoxyalkylenes, azide substituted alcohols, azide substituted alkanes, azide substituted alkenes, diazido alkanes and azide-substituted dyes.

In the above formula, R, R', R'', R ₁ and R ₂ are hydrogen atom, oxygen atom, nitrogen atom, fluorine atom, sulfur atom, sodium sulfate (SO ₃ Na), substituted or unsubstituted C ₁ to C ₃₀ may be independently selected from saturated aliphatic and C ₁ to C ₃₀ unsubstituted unsaturated aliphatic groups;

m, n, o and p are independently 0, 1, 2;

A and A ₁ are selected from an ether bond, an ester bond, an amide bond, a double bond, a triple bond, a C ₆ to C ₂₀ substituted or unsubstituted aromatic group, and a C ₆ to C ₂₀ substituted or unsubstituted heteroaromatic group can be at least one;

X may be one or more carbon atoms having a fluorine atom as a substituent.

Polyfunctional aziridine compounds include structures that have or can be derived from a general structure such as:

In the above formula, one or both of CH ₂ of aziridine may be substituted with, for example, methyl or a high molecular weight alkyl group. Although not particularly limited, the aziridine compound contains 3 to 5 nitrogen atoms per molecule. N such as N-amino ethyl-N-aziridyl ethyl amine, N,N-bis-2-amino propyl-N-aziridyl ethyl amine and N-3,6,9-triazanonyl aziridine -(amino alkyl) aziridine. Preferred crosslinking agents include bis- and tri-aziridine of di- and tri-acrylates of alkoxylated polyols including trisaziridine of triacrylates of adducts of glycerin and propylene oxide; trisaziridine of the tri-acrylate of the adduct of trimethylol propane and ethylene oxide; and tris-aziridine of a tri-acrylate of an adduct of pentaerythritol and propylene oxide, and typically 10 parts by weight or less based on 100 parts by weight of the organic binder. Preferably, within 0.02 to 5 parts by weight, more preferably 0.1 to 1.5 parts by weight may be added.

Specific examples of the aliphatic diamines include ethylene glycol diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[(2-aminomethoxy)ethyl]ether, Bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2- Aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3- Aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, methylenediamines ethylenediamine, 4,4-methylenebis(cyclohexanamine), 4,7 , 10-trioxa-1,13-tridecanediamine, 1,3-diamino-2-propanol, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1 ,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 3,5-diaminobenzoic acid, 2,4-diamino-6-hydroxypyrimidine, 4,4- Diaminostyrene-2,2-disulfonic acid, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,4-diaminocyclohexane, 1,12- Diamino dodecane etc. are mentioned. These aliphatic diamines may be one type or a mixture of two or more types.

Specific examples of the alicyclic diamine include isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1,8-diamino-p-mentane, 1,4-cyclohexanebis(methylamine), 1,3-Cyclohexanebis(methylamine), 2,5-diaminomethyl-bicyclo[2,2,2]octane, 2,5-diaminomethyl-7,7-dimethylbicyclo[2,2 ,1]heptane, 2,5-diaminomethyl-7,7-difluorobicyclo[2,2,1]heptane, 2,5-diaminomethyl-7,7,8,8-tetrafluorobicyclo [2,2,2]octane, 2,5-diaminomethyl-7,7-bis(hexafluoromethyl)bicyclo[2,2,1]heptane, 2,5-diaminomethyl-7-oxa Bicyclo[2,2,1]heptane, 2,5-diaminomethyl-7-thabicyclo[2,2,1]heptane, 2,5-diaminomethyl-7-oxobicyclo[2,2 ,1]heptane, 2,5-diaminomethyl-7-azabicyclo[2,2,1]heptane, 2,6-diaminomethyl-bicyclo[2,2,2]octane, 2,6-dia minomethyl-7,7-dimethylbicyclo[2,2,1]heptane, 2,6-diaminomethyl-7,7-difluorobicyclo[2,2,1]heptane, 2,6-diamino Methyl-7,7,8,8-tetrafluorobicyclo[2,2,2]octane, 2,6-diaminomethyl-7,7-bis(hexafluoromethyl)bicyclo[2,2,1 ]heptane, 2,6-diaminomethyl-7-oxybicyclo[2,2,1]heptane, 2,6-diaminomethyl-7-thiobicyclo[2,2,1]heptane, 2,6 -diaminomethyl-7-oxobicyclo[2,2,1]heptane, 2,6-diaminomethyl-7-iminobicyclo[2,2,1]heptane, 2,5-diamino-bicyclo [2,2,1]heptane, 2,5-diamino-bicyclo[2,2,2]octane, 2,5-diamino-7,7-dimethylbicyclo[2,2,1]heptane, 2,5-diamino-7,7-difluorobicyclo[2,2,1]heptane, 2,5-diamino-7,7,8,8-tetrafluorobicyclo[2,2,2] Octane, 2,5-diamino-7,7-bis(hexafluoromethyl)bicyclo[2,2,1]heptane, 2,5-diamino-7-oxabicyclo[2,2,1] Heptane, 2,5-diamino-7-thiabicyclo[2,2,1]heptane, 2,5-diamino-7-oxobicyclo[2,2,1]heptane, 2,5-diamino -7-azabicyclo[2,2,1] Heptane, 2,6-diamino-bicyclo[2,2,1]heptane, 2,6-diamino-bicyclo[2,2,2]octane, 2,6-diamino-7,7-dimethyl Bicyclo[2,2,1]heptane, 2,6-diamino-7,7-difluorobicyclo[2,2,1]heptane, 2,6-diamino-7,7,8,8- Tetrafluorobicyclo[2,2,2]octane, 2,6-diamino-7,7-bis(hexafluoromethyl)bicyclo[2,2,1]heptane, 2,6-diamino-7 -oxybicyclo[2,2,1]heptane, 2,6-diamino-7-thiobicyclo[2,2,1]heptane, 2,6-diamino-7-oxobicyclo[2,2 ,1]heptane, 2,6-diamino-7-iminobicyclo[2,2,1]heptane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diamino Cyclohexane, 1,2-di(2-aminoethyl)cyclohexane, 1,3-di(2-aminoethyl)cyclohexane, 1,4-di(2-aminoethyl)cyclohexane, 4,4-methylene Bis(N,N-diglycidylaniline), 1,3-bis(4-aminophenoxy)benzene, bis(4-aminocyclohexyl)methane, bis(4-aminophenyl)sulfone, 2,6- Diaminopyridine, 3,5-diamino-1,2,4-triazole, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane , and bicyclo[2,2,1]heptanebismethylamine. These alicyclic diamines can be used individually or in mixture of 2 or more types.

Furthermore, the crosslinking agent comprises at least one or more of hydroxy, amide, thiol, imidazole, triazole, etc. as a reactive group for crosslinking in a substituted or unsubstituted aliphatic diol, a substituted or unsubstituted alicyclic diol or molecular structure copolymers and polymer resins, and the like. As specific examples, polystyrene copolymer containing an aryl group, hydroquinone, pyrogallol, polycaprolactone diol, 1,6-hexanediol, tri Ethylene glycol, tetraethylene glycol, hexaethylene glycol, pentaethylene glycol, poly(vinylphenol), phenolic resin, (hydroxypropyl)methyl cellulose, hypromellose, hypromellose phthalate, polysaccharides ), poly(vinyl alcohol), polyethyleneimine (PEI), catechol, dopamine, aziridine monomer, and epoxy monomer.

The crosslinking agent may be used as at least one or a combination of two or more thereof, and may be used in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight based on 100 parts by weight of the organic binder.

The acid catalyst constituting the functional organic layer formulation of the present invention serves to promote crosslinking, and is not particularly limited, but includes, for example, nitric acid, sulfuric acid, phosphoric acid, oxalic acid, hydrochloric acid, trifluoroacetic acid, Lewis acid, etc. and 0.0001 to 0.2 parts by weight, preferably 0.005 to 10 parts by weight based on 100 parts by weight of the organic binder.

In the present invention, the photoinitiator absorbs light over 360 nm to form a reactive radical, which induces polymerization by photopolymerization. On the other hand, the photo-acid generator absorbs light over 360 nm to generate an acid catalyst to promote cross-linking between the organic binder and the cross-linking agent, or induce cross-linking through selective light irradiation under a mask and implement a fine pattern of the primer layer. . Commercial photoinitiators and photoacid generators are not particularly limited, but for example, BASF's Irgacure series, Irgacure PAG family, etc. may be mentioned, and 10 to 100 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the crosslinking agent. It can be used in parts by weight.

In the present invention, the filler may be included as needed for the purpose of improving adhesive strength and improving heat dissipation properties. It is not particularly limited thereto, and specific examples thereof include silicon dioxide, aluminum hydroxide, potassium carbonate, titanium dioxide, aluminum oxide, magnesium hydroxide, magnesium carbonate, silicon carbide, barium sulfate, mica powder, silica powder, talc powder, carbon nanotubes. , boron nitride nanoparticles, graphite, graphene, nanocellulose, carbon black, at least one selected from kaolin, and may be used in an amount of 1 to 80 parts by weight based on 100 parts by weight of the total solid content of the formulation.

In the present invention, the metal element constituting the metal ion organic complex may be selected from silver, platinum, copper, tin, iridium, etc., and is preferably selected from silver and copper.

Examples of silver organic complexes include, but are not limited to, silver nitride, silver acetate, silver fluorine, 1,5-cyclooctadiene-hexafluoroacetylacetonatosilver(I) complex, 1,1,1 -Trifluoro-2,4-pentanedione natosilver (I) complex, 5,5-dimethyl-1,1,1-trifluoro-2,4-hexanedione natosilver (I) complex , 1- (4-methoxyphenyl) -4,4,4-trifluorobutanedione natosilver (I) complex, 5,5,6,6,7,7,8,8,9,9 ,10,10,11,11,12,12,12-heptadecafluordecane-2,4-dionenatosilver (I) complex, 1,1,2,2,3,3-heptafluoro- 7,7-dimethyl-4,6-octanedione natosilver (I) complex, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dionenatosilver (I) complex, 1,1,1,5,5,5-hexafluoropentane-2,4-dionetosilver (I) complex, 5,5,6,6,7,7,8 ,8,8-nonafluorooctane-2,4-dionenatosilver(I) complex, 5H,5H-perfluorononane-4,6-dionenatosilver(I) complex, 6H, 6H-perfluoro-undecane-5,7-dionenatosilver(I) complex, 8H,8H-perfluoropentadecane-7,8-dionenatosilver(I) complex, 6H,6H -Perfluoroundecane-5,7-dionenatosilver(I) complex, 1-phenyl-2H,2H-perfluorohexane-1,3-dionenatosilver(I) complex, 1- Phenyl-2H,2H-perfluoroundecane-1,3-dionenatosilver(I) complex, 5,6,6,6-tetrafluoro-5-(heptafluoropropoxy)hexane-2,4 -Dionnatosilver(I) complex, 1,1,5,5-tetrafluoropentane-2,4-dionetosilver(I) complex, 5,5,6,6,7,7 ,8,8,9,9,9-undecanefluoro-nonane-2,4-dionenatosilver (I) complex, ethyl 3-chloro-4,4,4-trifluoroacetoacetatosilver (I) complex, ethyl-4,4-difluoroacetoacetatosilver (I) complex, ethyl-4,4,4-trifluoroacetoacetatosilver (I) complex, isopropyl-4 ,4,4-trifluoroacetoacetato silver (I) complex, methyl-4,4,5,5,5-pentafluoro-3-ox Sopentanonatosilver(I) complex, ethyl-4,4,5,5,5-pentafluor-3-oxo-pentanonatosilver(I) complex and 1,1,1,5,5; 6,6,6-octafluoro-2,4-hexanedionatosilver (I) complex compound etc. are mentioned. The silver ion organic complex may be used alone or as a mixture of two or more kinds. The silver ion organic complex may be used in an amount of 0.0005 to 20 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total organic solid content of the total formulation.

In the present invention, the catalyst for electroless plating can form silver nanoparticles on the primer layer matrix at a temperature of 100 ^o C to 200 ^o C using the silver ion organic complex in an in-situ method, which is formed with palladium and A metal seed layer can be formed on the finely patterned primer using an electroless plating solution generally known in the art without using the same expensive electroless plating catalyst. If the content of the silver ion organic complex in the composition of the present invention is less than 0.0005 parts by weight, the amount of catalyst is not sufficient, so the deposition rate of metal during electroless plating is significantly slow, and a uniform metal thin film is formed on the primer pattern. difficult. On the other hand, when the amount of the silver ion organic complex exceeds 20 parts by weight, the storage property of the composition is lowered, which makes it difficult.

The solvent constituting the formulation of the present invention is not particularly limited, and for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, or propylene glycol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, or n-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, or tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, 3-methoxypropyl acetate, propylene glycol monomethyl ether, propylene glycol ethyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol ethyl ether; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ethetate, or propylene glycol ethyl ether acetate; At least one selected from the group consisting of amides such as N,N-dimethylacetamide, N,N-dimethylformamide, and acetonitride, or a combination thereof may be used.

Furthermore, the catalytically active layer formulation according to the present invention may include other additives as needed for the purpose of coating, improving adhesion, and improving pattern precision. The other additives are generally known in the art, and include, but are not limited to, for example, surfactants, surface modifiers, adhesion enhancers, wetting agents, dispersants, and the like.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and sorbitan trioleate; polyoxyethylene nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate; EF-Top (registered trademark) EF-301, the same EF-303, the same EF-352 [above, manufactured by Mitsubishima Material Electronics Co., Ltd.], Megapac (registered trademark) F-171, the same F-173 , copper R-08, copper R-30 [above, manufactured by DIC Corporation], Novec (registered trademark) FC-430, copper FC-431 [above, manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) Fluorine-type surfactants, such as AG-710 (made by Asahi Glass Co., Ltd.) and Sufflon (trademark) S-382 (manufactured by AGC Seimi Chemical Co., Ltd.), etc. are mentioned.

Moreover, as said surface conditioning agent, Silicone-type leveling agents, such as Shin-Etsu Silicone (trademark) KP-341 (made by Shin-Etsu Chemical Industry Co., Ltd.); Silicone-based surface conditioners such as BYK (registered trademark)-302, 307, 322, 323, 330, 333, 370, 375, 378 [above, made by Big Chemie Japan] can be heard

In the present invention, a wet type of substrate surface treatment is necessary and can be applied as an example, and a strong alkaline aqueous solution can be used as an example, but not limited thereto, but as a specific example of an alkali agent, sodium hydroxide, potassium hydroxide, etc. can be mentioned, and 0.1 to 2 molar concentrations.

In the surface treatment, another example may be a dry method, but is not limited thereto, and may include arc plasma pretreatment, oxygen plasma pretreatment, UV/ozone treatment, and the like.

In the present invention, the catalytically active layer formulation may be applied by a wet thin film coating method, but is not particularly limited, but as a specific example, a spin coating method; blade coat method; dip coating method; roll coat method; barcoat method; die coat method; A thin film is formed by coating by a spray coating method or the like, and then evaporating and drying the solvent.

In the present invention, by performing an electroless plating method on the catalytically active layer formed on the substrate obtained as described above, a metal plating film is formed thereon. The electroless plating treatment (process) is not particularly limited, and can be performed by any generally known electroless plating treatment. For example, a conventionally generally known electroless plating solution is used and immersed in this plating solution (bath). How to do it is common

The electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and according to other uses, a pH adjuster, a pH buffer, a reaction accelerator (second complexing agent), a stabilizer, a surfactant (for the plating film) The use of glossing, the use of improving the wettability of the surface to be treated, etc.) are included as appropriate.

Examples of the metal used for the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold and alloys thereof, and is appropriately selected according to the purpose. .

Example

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited thereto. In the Examples, the reagents and peel strength measuring tools used were performed based on the following conditions.

Polyimide film: DuPont, 35 microns

Potassium Hydroxide (KOH): Sigma Aldrich

(hydroxypropyl)methyl cellulose (HPMC): Sigma Aldrich

Bisphenol A diglycidyl ether: Sigma Aldrich

Ethylene glycol diglycidyl ether: Sigma Aldrich

PGME (1-methoxy-2-propanol): Sigma Aldrich

AgNO ₃ : Sigma Aldrich

1,6-hexandiol: Sigma Aldrich

Laromer: BASF SE (resin based on acrylic)

Irgacure PAG 169: BASF SE

Irgacure 184: BASF SE

1,6-hexandiol: Sigma Aldrich

Cu etchant: Sigma Aldrich

Alkaline developer: 2.38% TMAH solution (Merck)

The present inventors manufactured a fine metal pattern on one surface of a polyimide film having surface defects through the following process. First, the surface of the film was supported in a 1.0 M KOH aqueous solution at 50 ^o C for 5 minutes, washed several times with distilled water, and dried at 120 ^o C for 10 minutes. Thereafter, the functional undercoat formulation shown in Table 1 below was spin-coated at 3000 rpm for 10 seconds, and heated for 30 minutes in a heater heated to 170 ^° C. after UV irradiation to form a 1.0 micron thick functional undercoat film. Then, the photosensitive primer formulation shown in Table 2 is applied to the upper portion of the functional undercoat layer, irradiated with ultraviolet light under a mask (60 mJ/cm ² ), and baked at 100 ^o C for several minutes. After that, it was developed with PGME solvent and washed several times with distilled water at room temperature. After that, baking treatment is performed in a 150 ^o C heater to form a silver catalyst inside the primer layer. Next, a copper layer (8 microns) was formed with an electroless and electrolytic plating solution to finally complete the fabrication of a fine metal pattern.

In the case of manufacturing the narrow tooth pattern, the thickness of the prepared plating layer is adjusted to 0.5 um. Spin coating a positive photoresist on top of the plating layer at 2,000 rpm for 30 seconds, baking at 100 ^o C for 5 minutes, and irradiating 360 nm light for 2 seconds under a mask ((60 mJ/cm ² ). Next, with an alkaline developer Develop the exposed part and dry it.Copper layer is selectively formed on the developed part by electroplating method, and finally a copper layer with a thickness of 10 μm is prepared.After that, the photoresist layer is removed and the copper layer of the thin film is removed. It is removed using Cu etchant, and dried at 120 ^o C for 1 hour to finally complete the fabrication of a fine metal pattern.

In Table 3 below, the peeling properties of the metal pattern were analyzed with an optical microscope while completing the fabrication of the fine metal pattern and repeating the peel-off test with an adhesive tape (3M).

In conclusion, it was confirmed that, in the case of a fine metal pattern, even after repeated peel-off tests, it had stable adhesion properties even in a fine pattern of 10 μm or less.

Claims (12)

A flexible metal foil film having high peel strength characteristics, a thin functional undercoat and primer formation on one or both sides of a substrate, and at least one selected from iron, cobalt, nickel, copper, silver, gold, aluminum, and tin on top of the primer A flexible copper foil film composed of a metal or an alloy thereof.
The flexible copper foil film according to claim 1, wherein the functional undercoat and the primer include a polymer resin layer that can be prepared by a photopolymerizable binder, an organic binder that can be thermally cured or crosslinked.
The flexible copper foil film according to claim 1, wherein the metal layer is prepared by an electroless plating method or an electrolytic plating method alone or a combination thereof.
According to claim 2, wherein the polymer resin is polyethyleneimine, urea resin, phenol resin, alkylated melamine resin, polyurethane, polyamic acid, polyimide, polyvinyl alcohol, polyvinyl phenol, (hydroxypropyl) methyl cellulose, hypmellose (hypromellose), hypromellose phthalate, polysaccharides, resins prepared by polyfunctional monomers having aziridine or glycidyl groups, polyfunctional monomers or oligomers having unsaturated ethylene groups Flexible copper foil, characterized in that it is selected from at least one or a combination of resins prepared by film.
According to claim 2, wherein the crosslinking agent for crosslinking is a compound having a molecular weight within 50 to 1,000, polyfunctional azide or aziridine compound, substituted or unsubstituted aliphatic diamine, substituted or unsubstituted alicyclic diamine, substituted or Unsubstituted aliphatic diol, substituted or unsubstituted alicyclic diol, substituted or unsubstituted alkylated melamine resin having a molecular weight of 300 to 100,000, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, A flexible copper foil film, characterized in that it is selected from one or a combination of ethylene urea-formaldehyde resins, and is 1 to 50 weight percent of the total solid content of the formulation.
According to claim 1, wherein the functional undercoat and primer may further include a filler if necessary, silicon dioxide, aluminum hydroxide, potassium carbonate, titanium dioxide, aluminum oxide, magnesium hydroxide, magnesium carbonate, silicon carbide, barium sulfate , mica powder, silica powder, talc powder, carbon nanotubes, boron nitride nanoparticles, graphite, carbon black, flame retardant, at least one selected from kaolin, and 0.5 to 80 weight percent of the total solid content of the formulation ductility, characterized in that copper foil film.
According to claim 1, wherein the functional undercoat and primer may further include a metal ion organic complex, 0.0005 to 20 parts by weight, preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total organic solid content of the total formulation. Flexible copper foil film, characterized in that it can be used within parts.
The flexible copper foil film according to claim 1, wherein the coating thickness of the functional undercoat and the primer is independently 5 nm to 5 um, preferably 50 nm to 1 um, more preferably 100 nm to 500 nm.
According to claim 1, wherein the substrate has a glass transition temperature in the range of 80 ^o C to 400 ^o C, preferably polyester (PET), polyester naphthalene (PEN), polycyclohexylene dimethylene terephthalate (PCT), liquid crystal A flexible copper foil film, characterized in that at least one selected from polymer (LCP), yellow and black polyimide (PI), and polyphenylsulfonyl (PPS).
10. The method according to claim 1 to 9, characterized in that the copper layer thickness of the prepared flexible metal foil film is 0.05 um to 100 um, preferably 0.5 um to 50 um, more preferably 1 um to 25 um Flexible copper foil film.
A method for manufacturing a flexible copper foil film, comprising:
Step 1: attaching dry film resist (DFR) or applying photoresist on the upper part of the metal foil having a thickness of 0.1 to 1 um;
Second step: selective exposure and development under masking;
3rd step: selective plating by electrolytic plating method on the exposed part;
Fourth step: DFR or photoresist removal step; and
Step 5: A method for manufacturing a flexible copper foil film comprising the step of removing the lower metal foil by wet or dry etching.
The method of claim 11, wherein the fine metal pattern has a pitch of 5 um to 500 um.

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