KR102710371B1 - Flexible copper foil film and manufactruing method thereof - Google Patents

Abstract

The present invention relates to a method for producing a conductive metal layer or a fine metal pattern that can be used in electrode systems of various electronic devices, optical sensors and conductive films, printed circuits and semiconductor packaging substrates, and more particularly, to a flexible copper-clad laminate film having high peel strength characteristics, in which a functional undercoat and primer in the form of a thin film are applied to one or both sides of any substrate by a wet process, and at least one metal selected from iron, cobalt, nickel, copper, silver, gold, aluminum and tin or an alloy thereof is formed on the primer, and further to the production of a fine metal pattern.

Description

FLEXIBLE COPPER FOIL FILM AND MANUFACTRUING METHOD THEREOF

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

As the need for lightweight, compact, and high-performance electronic devices and systems increases, various material technologies and electrode wiring technologies are required to implement them. For example, in the case of manufacturing sensor and semiconductor packaging substrates and printed circuit boards, a method of implementing a metal circuit pattern by forming a circuit pattern of a certain shape on a copper film (copper foil) laminated with an adhesive on a heat-resistant substrate or a thin copper film physically deposited using a classical photolithography process and then etching the copper to manufacture a metal circuit pattern is generally used. This traditional metal circuit pattern formation technology is complicated and requires expensive equipment investment and also has environmental pollution problems due to the generation of corrosive etching solutions. At the same time, implementing a fine circuit pattern requires additional investment in expensive materials and expensive, precise equipment.

On the other hand, a method of forming surface roughness on the surface of a substrate through a desmear process for fine wiring and forming a conductor layer on the insulating layer on which the surface roughness has been 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 increases, but the problem of making fine wiring difficult occurs. In addition, if the surface roughness is lowered for fine wiring, the problem of reducing the adhesion strength occurs.

Therefore, surface roughness and adhesive strength are in a trade-off relationship, and a method is needed that secures adhesive strength between the substrate and the conductive layer while maintaining surface roughness refinement and enables implementation of fine wiring.

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

Accordingly, the present invention has taken note of the problems found in the above literature, and aims to provide a flexible metal foil film that is more environmentally friendly, has low production process cost, and has high peel strength characteristics, by applying a catalytic active layer capable of electroless plating on a target substrate by a low-cost wet thin-film coating process, flattening a surface-defective portion, and forming a metal thin film layer on top of the same by using an electroless plating method. In addition, the present invention aims to provide a flexible metal foil film that applies the existing photolithography process in the subsequent process of manufacturing a slit pattern and has excellent pattern precision.

In order to achieve the above object, the present invention was completed by manufacturing a catalytic active material by 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 the same on a substrate to obtain a catalytic active layer capable of refining the surface roughness of the substrate, finding that the plating property by an electroless plating method on the upper part is excellent, and that the adhesion between the metal plating film and the plated substrate is excellent. Furthermore, in the case of manufacturing a coherent pattern of a plating layer by a photolithography method, it was found that manufacturing a metal pattern having an excellent pattern precision of a line width of 10 um or less is possible.

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

Or, it is characterized in that the above catalytic active layer is manufactured by a combination comprising a photopolymerizable binder, a metal ion organic complex, a filler, a photoinitiator, and an organic solvent.

The above catalyst active layer is characterized in that the thickness is 2 nm to 20 um, preferably 50 nm to 10 um, and more preferably 500 nm to 2 um.

The above-mentioned cooperation pattern is characterized in that it is manufactured by a photolithography method.

The present invention eliminates the physical deposition of prior patents and enables the flattening of surface defects of a substrate by a catalytic active layer based on a wet coating technique, and can exhibit the effects of excellent adhesive strength between a substrate and a plating metal layer and low-cost implementation of a fine metal pattern.

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

Hereinafter, the present invention will be described in detail.

The present invention The present invention relates to a flexible metal foil film having high peel strength characteristics, which comprises a catalytically active layer applied on one or both sides of a substrate by a wet process and is composed of at least one metal selected from iron, cobalt, nickel, copper, silver, gold, aluminum, and tin, or an alloy thereof, on the upper side thereof, and to the manufacture of a pattern formed thereon by a photolithography method.

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

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

Or, it is characterized in that the above catalytic active layer is manufactured by a combination comprising 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 heat resistance, chemical resistance, improved adhesive strength, and excellent developability for producing fine patterns. Copolymer resins prepared by including 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, 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, Copolymer resins manufactured by including maleimide monomers such as 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-phenyl)-pyrrole-2,5-dione, alkylated melamine resins, phenol resins, urea resins, urethane series resins, polypyrrolidinone, polyvinylphenol, polyvinyl alcohol, polystyrene, polymetamethyl acetate, polyvinylacetate, polyamic acid, soluble polyimide, etc. can be used.

In particular, it is preferable to use polyvinylphenol or alkylated melamine resins, such as poly(4-vinylphenol), alone or in combination, for the purpose of improving the insulation, heat resistance and chemical resistance of the organic layer. The available alkylated melamine resin is selected from melamine resins, or cocondensates, 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, trimethylol melamine trimethyl ether, tetramethylol melamine 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, and ethoxymethylmelamines corresponding thereto. Examples thereof include alkoxymethylmelamines such as butoxymethylmelamine. Furthermore, it may have heterogeneous alkoxymethyl groups such as a methoxymethyl group, an ethoxymethyl group, and a butoxymethyl group on the same melamine nucleus. In addition, it may be a multimerized one by a methylene bond, a dimethylene ether bond, or the like. The alkylated melamine resin usually has at least 3 or more, preferably 4 to 6, alkoxymethyl groups per melamine nucleus, and hexakismethoxymethylmelamine is particularly preferred. These do not necessarily have to be a single compound, and may be a mixture of two or more.

In the present invention, the photopolymerizable binder is not particularly limited, and for example, a polyfunctional monomer containing an ethylenically unsaturated bond, and is not limited thereto, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate having 2 to 14 ethylene groups, or polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, propylene glycol diacrylate having 2 to 14 propylene groups, or propylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, Examples thereof include compounds obtained by esterifying a polyhydric alcohol such as dipentaerythritol hexamethacrylate with an α, β-unsaturated carboxylic acid; compounds obtained by adding acrylic acid or methacrylic acid to a compound containing a glycidyl group such as a trimethylolpropane triglycidyl ether acrylic acid adduct or a bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group or ethylenically unsaturated bond such as a phthalic acid ester of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate, a toluene diisocyanate adduct of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate, and a carboxylic acid having multiple carboxyl groups, or adducts of a compound having a hydroxyl group or ethylenically unsaturated bond and a multi-isocyanate. The above ethylenically unsaturated bond-containing polyfunctional monomer can be used alone or in combination of two or more kinds of mixtures. The above ethylenically unsaturated bond-containing polyfunctional monomer is preferably one having three or more functional groups having ethylenically unsaturated bonds in terms of the shape of the fine pattern and chemical resistance and adhesive properties during electroless plating. In addition, examples thereof include, but are not limited to, monomers having an aziridine structure with a polyfunctional group and monomers capable of crosslinking by a condensation reaction.

In the present invention, the type of crosslinking agent is not particularly limited, but may be selected from compounds having a molecular weight of 50 to 1,000, compounds having a polyfunctional azide and polyfunctional aziridine group, substituted or unsubstituted aliphatic diamine, 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 copolymers and polymer resins containing at least one hydroxyl, amide, thiol, imidazole, triazole, etc. as a reactive group for crosslinking within the molecular structure.

The polyfunctional azide compounds are not particularly limited and generally include hydrophilic organic azido groups, hydrophobic organic azido groups (including amphiphilic organic azido groups), diazido organic bridging groups and azide-substituted aromatic derivatives, including but not limited to any of the structures exemplified in Formulae 1 to 6. Examples of suitable azide-substituted organic compounds can include azide-substituted polyoxyalkylenes, azide-substituted organic amines (and ammonium salts thereof), azide-substituted organic amides, azide-substituted organic imines, azide-substituted carboxylic acids, azide-substituted carbonyl compounds (e.g., 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 chemical formula, R, R', R'', R ₁ and R ₂ can be independently selected from a hydrogen atom, an oxygen atom, a nitrogen atom, a fluorine atom, a sulfur atom, sodium sulfate (SO ₃ Na), a substituted or unsubstituted C ₁ to C ₃₀ saturated aliphatic, a C ₁ to C ₃₀ unsubstituted unsaturated aliphatic group group;

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

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

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

Multifunctional aziridine compounds include those having the general structure of chemical formula 7 or structures derived therefrom:

In the above chemical formula, one or both of the CH ₂ of the aziridine may be substituted, for example, with methyl or a high molecular weight alkyl group. Although not particularly limited, the aziridine compound contains 3 to 5 nitrogen atoms per molecule. Examples include N-(amino alkyl) aziridines 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. Preferred crosslinkers are bis- and tri-aziridines of di- and tri-acrylates of alkoxylated polyols including trisaziridines of the triacrylates of the adducts of glycerin and propylene oxide; trisaziridines of the triacrylates of the adducts of trimethylol propane and ethylene oxide; And may include tris-aziridine of tri-acrylate of adduct of pentaerythritol and propylene oxide, and can be added typically at 10 parts by weight or less per 100 parts by weight of organic binder. Preferably, it is within 0.02 to 5 parts by weight, and more preferably, 0.1 to 1.5 parts by weight can be added.

Specific examples of aliphatic diamines include ethylene glycol diamines, 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, and methylene diamines, ethylenediamine, Examples thereof include 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, and 1,12-diaminododecane. These aliphatic diamines may be used alone or in a mixture of two or more.

Specific examples of alicyclic diamines include, for example, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1,8-diamino-p-menthane, 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-oxabicyclo[2,2,1]heptane, 2,5-diaminomethyl-7-thiabicyclo[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-diaminomethyl-7,7-dimethylbicyclo[2,2,1]heptane, 2,6-diaminomethyl-7,7-difluorobicyclo[2,2,1]heptane, 2,6-diaminomethyl-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[2,2,1]heptane, 2,6-diamino-bicyclo[2,2,2]octane, 2,6-diamino-7,7-dimethylbicyclo[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-diaminocyclohexane, 1,2-di(2-aminoethyl)cyclohexane, 1,3-di(2-aminoethyl)cyclohexane, Examples thereof include 1,4-di(2-aminoethyl)cyclohexane, 4,4-methylenebis(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 singly or in a mixture of two or more.

Furthermore, the crosslinking agent may include a substituted or unsubstituted aliphatic diol, a substituted or unsubstituted alicyclic diol, or a copolymer and a polymer resin containing at least one hydroxy, amide, thiol, imidazole, triazole, etc. as a reactive group for crosslinking within the molecular structure, as specific examples thereof, a polystyrene copolymer containing an aryl group, hydroquinone, pyrogallol, polycaprolactone diol, 1,6-hexanediol, triethylene glycol, tetraethylene glycol, hexaethylene glycol, pentaethylene glycol, poly(vinylphenol), a phenol resin, (hydroxypropyl)methyl cellulose, hypromellose, hypromellose phthalate, polysaccharides, poly(vinyl alcohol), polyethyleneimine (PEI), catechol, dopamine, aziridine monomer, epoxy monomer, etc. Can be.

The above cross-linking agent can be used in at least one or a combination of two or more thereof and can be used in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, per 100 parts by weight of the organic binder.

The acid catalyst constituting the functional organic layer combination of the present invention serves to promote crosslinking, and is not particularly limited, but examples thereof include nitric acid, sulfuric acid, phosphoric acid, oxalic acid, hydrochloric acid, trifluoroacetic acid, Lewis acid, etc., and can be used in an amount of 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 of 360 nm or more to form a reactive radical, which induces polymerization by a photopolymerization reaction. On the other hand, the photoacid generator absorbs light of 360 nm or more to generate an acid catalyst to promote crosslinking between the organic binder and the crosslinking agent, or induces crosslinking through selective light irradiation under a mask to implement a fine pattern of the primer layer. There is no particular limitation on commercial photoinitiators and photoacid generators, but examples thereof include the Irgacure series and the Irgacure PAG product line of BASF, and can be used in an amount of 10 to 100 parts by weight, preferably 50 to 80 parts by weight, based on 100 parts by weight of the crosslinking agent.

In the present invention, fillers may be included as needed for the purpose of improving adhesive strength and heat dissipation characteristics. The filler is not particularly limited thereto, and as specific examples, at least one is selected from among 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, and 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 blend.

In the present invention, the metal element constituting the metal ion organic complex can 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-pentanedionatosilver(I) complex, 5,5-dimethyl-1,1,1-trifluoro-2,4-hexanedionatosilver(I) complex, 1-(4-methoxyphenyl)-4,4,4-trifluorobutanedionatosilver(I) complex, 5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorodecane-2,4-dionatosilver(I) complex, 1,1,2,2,3,3-Heptafluoro-7,7-dimethyl-4,6-octanedionatosilver(I) complex, 1,1,1,3,5,5,5-Heptafluoropentane-2,4-dionatosilver(I) complex, 1,1,1,5,5,5-Hexafluoropentane-2,4-dionatosilver(I) complex, 5,5,6,6,7,7,8,8,8-Nonafluorooctane-2,4-dionatosilver(I) complex, 5H,5H-Perfluorononane-4,6-dionatosilver(I) complex, 6H,6H-Perfluoro-undecane-5,7-dionatosilver(I) complex, 8H,8H-Perfluoropentadecane-7,8-dionnatosilver(I) complex, 6H,6H-Perfluoroundecane-5,7-dionnatosilver(I) complex, 1-phenyl-2H,2H-perfluorohexane-1,3-dionnatosilver(I) complex, 1-phenyl-2H,2H-perfluoroundecane-1,3-dionnatosilver(I) complex, 5,6,6,6-tetrafluoro-5-(heptafluoropropoxy)hexane-2,4-dionnatosilver(I) complex, 1,1,5,5-tetrafluoropentane-2,4-dionnatosilver(I) complex, 5,5,6,6,7,7,8,8,9,9,9-undecanefluoro-nonane-2,4-dionetosilver(I) complex, ethyl 3-chloro-4,4,4-trifluoroacetoacetate silver(I) complex, ethyl-4,4-difluoroacetoacetate silver(I) complex, ethyl-4,4,4-trifluoroacetoacetate silver(I) complex, isopropyl-4,4,4-trifluoroacetoacetate silver(I) complex, methyl-4,4,5,5,5-pentafluoro-3-oxopentanonato silver(I) complex, ethyl-4,4,5,5,5-pentafluoro-3-oxoopentanonato silver(I) complex and Examples thereof include 1,1,1,5,5,6,6,6-octafluoro-2,4-hexanedionatosilver(I) complex, etc. The above silver ion organic complexes may be used alone or in combination of different or more kinds. The above silver ion organic complexes 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 entire formulation.

In the present invention, the catalyst for electroless plating is capable of forming silver nanoparticles in situ on a primer layer matrix at a temperature of 100 ^o C to 200 ^o C using the silver ion organic complex, and this can form a metal seed layer on a finely patterned primer using an electroless plating solution generally known in this technical field without using an expensive electroless plating catalyst such as palladium. If the content of the silver ion organic complex in the composition of the present invention is less than 0.0005 part by weight, the amount of the catalyst is not sufficient, so that the deposition speed of the metal during electroless plating is significantly slow, and it is difficult to form a uniform metal film on the primer pattern. On the other hand, if the amount of the silver ion organic complex exceeds 20 parts by weight, the storability of the composition deteriorates, which becomes difficult.

The solvent constituting the combination of the present invention is not particularly limited, and includes, 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; Acets such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, or propylene glycol ethyl ether acetate; amides such as N,N-dimethylacetamide, N,N-dimethylformamide, and acetonitride; and the like can be used at least one or a combination thereof.

Furthermore, the catalyst active layer composition according to the present invention may contain other additives as needed for the purposes of coating, improving adhesion, and improving pattern precision. The other additives are those generally known in this technical field, and include, but are not limited to, surfactants, surface conditioners, 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. Examples thereof include fluorine-based surfactants, such as Ep-Top (registered trademark) EF-301, EF-303, and EF-352 [all manufactured by Mitsubishi Material Electro-Chemicals Co., Ltd.], Megapak (registered trademark) F-171, F-173, R-08, and R-30 [all manufactured by DIC Co., Ltd.], Novec (registered trademark) FC-430, FC-431 [all manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) AG-710 [manufactured by Asahi Glass Co., Ltd.], and Surflon (registered trademark) S-382 [manufactured by AGC Seimi Chemical Co., Ltd.].

In addition, examples of the surface conditioner include silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 [manufactured by Shin-Etsu Chemical Co., Ltd.]; silicone-based surface conditioners such as BYK (registered trademark)-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 [all manufactured by BYK Chemie Japan Co., Ltd.];

In the present invention, wet method surface treatment of the substrate is required and can be applied, and as an example, a strongly alkaline aqueous solution can be used, and although not limited thereto, specific examples of alkaline agents include sodium hydroxide, potassium hydroxide, etc., and can be used at a concentration of 0.1 to 2 molar.

Other examples of the above surface treatment include dry methods, but are not limited to arc plasma pretreatment, oxygen plasma pretreatment, and UV/ozone treatment.

In the present invention, the catalyst active layer composition can be applied by a wet thin film coating method, and is not particularly limited thereto, but specific examples thereof include a spin coating method; a blade coating method; a dip coating method; a roll coating method; a bar coating method; a die coating method; a spray coating method, etc., and then the solvent is evaporated and dried to form a thin film.

In the present invention, by performing an electroless plating method on the catalyst active layer formed on the substrate obtained as described above, a metal plating film is formed on the upper portion. The electroless plating treatment (process) is not particularly limited, and can be performed by any electroless plating treatment generally known. For example, a method of immersing in a plating solution (bath) using a conventionally known electroless plating solution is generally used.

The above electroless plating solution mainly contains metal ions (metal salts), a complexing agent, and a reducing agent, and other agents such as a pH adjuster, a pH buffer, a reaction accelerator (second complexing agent), a stabilizer, and a surfactant (for use in imparting gloss to a plating film, improving wettability of a surface to be treated, etc.) are appropriately added according to the intended use.

Here, metals used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and are appropriately selected depending on the purpose.

Example

Hereinafter, the present invention will be described more specifically 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 micron

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 (acrylic-based resin)

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 inventors of the present invention manufactured a fine metal pattern on one side of a polyimide film having surface defects through the following process. First, the surface of the film was immersed 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 compositions presented in Table 1 were spin-coated at 3000 rpm for 10 seconds, irradiated with ultraviolet rays, and heated in a heater heated to 170 ^o C for 30 minutes to form a functional undercoat film having a thickness of 1.0 micron. Then, the photosensitive primer compositions presented in Table 2 were applied on the functional undercoat layer, irradiated with ultraviolet rays (60 mJ/cm ² ) under a mask, and baked at 100 ^o C for several minutes. Thereafter, the film was developed with a PGME solvent and washed several times with distilled water at room temperature. After this, the silver catalyst is formed inside the primer layer by baking in a 150 ^o C heater. Next, a copper layer (8 microns) is formed using an electroless and electrolytic plating solution to finally complete the production of a fine metal pattern.

In the case of manufacturing a cooperation pattern, the thickness of the manufactured plating layer is adjusted to 0.5 μm. A positive photoresist is spin-coated on the plating layer at 2,000 rpm for 30 seconds, baked at 100 ^o C for 5 minutes, and irradiated with 360 nm light for 2 seconds ((60 mJ/cm ² )) under a mask. Next, the exposed portion is developed with an alkaline developer and dried. A copper layer is selectively formed on the developed portion by an electrolytic plating method to finally manufacture a copper layer with a thickness of 10 μm. Thereafter, the photoresist layer is removed, and the thin copper layer is removed using a Cu etchant. The fine metal pattern is finally manufactured by drying at 120 ^o C for 1 hour.

Table 3 below summarizes the results of analyzing the peeling characteristics of the metal pattern using an optical microscope while performing repeated peel-off tests with adhesive tape (3M) after completing the production of the fine metal pattern.

In conclusion, it was confirmed that even for fine metal patterns of less than 10 μm, stable adhesion properties were maintained even after repeated peel-off tests.

.

Claims (13)

delete A substrate; a functional undercoat formed on the substrate; a catalytically active layer formed on the functional undercoat; and a metal layer formed on the catalytically active layer including a metal component;
The above catalytic active layer is,
formed by including an organic binder; or a photopolymerizable binder;
The above functional undercoat is,
Hydroxypropyl methylcellulose (HPMC); and
A flexible metal foil laminate film formed by including 1,6-hexanediol.
In the second paragraph,
The above metal layer,
Including being formed to be directly bonded to one surface of the above catalyst active layer,
A flexible metal foil laminate film formed by electroless plating.
In the second paragraph,
The above organic binder,
A flexible metal foil laminate film comprising a copolymer resin manufactured including a carboxyl group monomer; a copolymer resin manufactured including a maleimide monomer; an alkylated melamine resin; a phenol resin; a urea resin; a urethane series resin; a polypyrrolidinone; a polyvinylphenol; a polyvinyl alcohol; a polystyrene; a polymethylene terephthalate; a polyvinyl acetate; a polyamic acid; or a soluble polyimide.
In the second paragraph,
The above catalyst active layer further comprises a cross-linking agent,
The above cross-linking agent is,
A compound having a molecular weight of 50 to 1,000, a compound having a polyfunctional azide group and a polyfunctional aziridine group; a substituted or unsubstituted aliphatic diamine; a substituted or unsubstituted alicyclic diamine; a substituted or unsubstituted alkylated melamine resin having a molecular weight of 300 to 100,000; an unsubstituted aliphatic diol; a substituted or unsubstituted alicyclic diol; or a copolymer including at least one selected from hydroxy, amide, thiol, imidazole, and triazole as a reactive group for crosslinking within the molecular structure;
The above cross-linking agent is,
A flexible metal foil laminate film, wherein the amount is 1 to 50 parts by weight based on 100 parts by weight of the organic binder.
In the second paragraph,
The above catalytic active layer is formed by further including a filler,
The above filler is,
A flexible metal foil laminate film comprising at least one selected from 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, and kaolin.
In the second paragraph,
The above catalytic active layer is formed by further including a metal ion organic complex,
The above metal ion organic complex is,
A flexible metal foil laminate film, wherein the amount of the organic binder is 0.0005 to 20 parts by weight based on 100 parts by weight of the total organic binder.
In the second paragraph,
A flexible metal foil laminate film, wherein the thickness of the catalytic active layer is 2 nm to 20 um.
In the second paragraph,
The above description,
The glass transition temperature is 80 to 400℃,
A flexible metal foil laminated film made of a material of 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, phenol resin series, melamine series, or polyamide (PA) series.
In the second paragraph,
The above photopolymerizable binder,
Containing a polyfunctional monomer containing ethylenically unsaturated bonds,
The above ethylenically unsaturated bond-containing polyfunctional monomer is,
A flexible metal foil laminate film having a functional group having ethylenically unsaturated bonds of 3 or more.
In the second paragraph,
The above organic binder comprises an alkylated melamine resin,
The above alkylated melamine resin is,
A flexible metal foil laminate film comprising methoxymethylmelamine, alkoxymethylmelamine, or hexakismethoxymethylmelamine.
In Article 7,
A flexible metal foil laminate film, wherein the metal element constituting the above metal ion organic complex is silver nanoparticles.
A method for manufacturing a fine metal pattern of a flexible metal foil laminate film,
A step of coating a photoresist on a metal layer (hereinafter referred to as “first metal layer”) of a flexible metal foil laminate film according to any one of claims 2 to 12;
A step of selectively exposing and developing the photoresist under a mask;
A step of forming a second metal layer using plating on the developed portion;
a step of removing the above photoresist; and
A method for manufacturing a fine metal pattern of a flexible metal foil laminate film, characterized by including a step of removing a part of the first metal layer by using etching.