KR20220093615A - Conductive metal layer, fine metal pattern, and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a conductive metal layer or a method for manufacturing a fine metal pattern, which can be used for an electrode system, an optical sensor, and a conductive film of a variety of electronic devices, a printed circuit, and a semiconductor packaging substrate. The conductive metal layer of the present invention is a three-layered structure consisting of (i) a functional undercoat, (ii) a primer layer, and (iii) at least one metal selected from iron, cobalt, nickel, copper, palladium, silver, tin, platinum, and gold or an alloy thereof, based on any substrate. According to the present invention, physical deposition of a prior patent is excluded and instead based on a wet coating method, provided is an effect of implementing a fine metal pattern which can flatten a defect on a surface of the substrate by the functional undercoat of the thin film and the primer, provide excellent adhesion strength with the substrate, and further have high stripping strength caused by a low-cost plating method.

Description

Conductive metal layer, fine metal pattern and manufacturing method thereof

The present invention relates to the production of conductive metal layers or fine metal patterns that can be used in electrode systems, optical sensors and conductive films, printed circuits and semiconductor packaging substrates of various electronic devices, and conductive laminates formed on one or both sides on any substrate or The conductive micropattern lamination is made of (i) a functional undercoat, (ii) a primer layer, (iii) at least one metal selected from iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, or an alloy thereof. It is characterized in that it is composed of a three-layer structure.

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 realizing a metal circuit pattern in the case of manufacturing a sensor, a semiconductor packaging substrate, and a 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, in realizing the microcircuit pattern, additional investment in expensive and precise equipment is required along with expensive materials.

On the other hand, in order to provide excellent peel strength between the insulating substrate layer and the copper layer, a method of forming a surface roughness on the surface of the substrate through a desmear process and forming a conductor layer on the insulating substrate 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 functional undercoat having excellent heat resistance on a target substrate by a low-cost wet thin film coating process method to flatten the surface defect portion, and includes a metal ion complex and introduction of a primer capable of fine patterning, and finally, a mixture of electroless or electrolytic plating methods on the patterned primer to form a fine metal pattern, making it more eco-friendly, low production process cost, excellent adhesion, and non-conductive with pattern precision An object of the present invention is to provide metal foil and conductive micro-patterns on a substrate, and furthermore, various electronic device electrodes using the same, conductive films, solar systems, next-generation battery electrodes and sensors, printed circuits, and next-generation semiconductor packaging substrates.

In order to achieve the above object, to obtain a formulation that may further include an organic binder, a crosslinking agent, an acid catalyst, an organic solvent and a filler if necessary, and applying it on a substrate, a functional undercoat layer obtained with excellent heat resistance and excellent heat resistance and interaction with the substrate that it has high adhesive strength and that the surface roughness of the substrate can be refined. Here, a photosensitive primer layer containing a photoacid generator, a specific cross-linking binder and a cross-linking agent can be finely patterned by photolithography or inkjet process, and electroless plating or electrolytic plating is mixed on top of the patterned primer layer. The present invention was completed by discovering that the plating property was excellent and the adhesion between the metal plating film and the substrate to be plated was excellent.

It is characterized in that the thickness of the functional undercoat layer is 2 nm to 20 um, preferably 50 nm to 10 um, more preferably 100 nm to 2 um.

It is characterized in that the thickness of the primer layer is 2 nm to 10 um, preferably 10 nm to 5 um, more preferably 20 nm to 1 um.

The fine metal pattern electrode is characterized in that it is manufactured through a mixture of electroless plating or electroplating process directly on the fine patterned primer layer by photolithography, inkjet and printing processes.

By the present invention, physical vapor deposition of prior patents is excluded, surface defects of the substrate can be planarized by a functional undercoat and primer of a thin film based on wet coating technique, excellent adhesive strength with the substrate is provided, and furthermore, a low-cost plating method is used It is possible to show the effect of realizing a fine metal pattern having high peel strength characteristics by

1 is a simple cross-sectional view of a fine metal pattern structure formed on one or both surfaces of a substrate.
2 is an illustration of a method of manufacturing a fine metal pattern on a substrate with surface defects.
3 is an example of a method of manufacturing a fine metal pattern by a photolithography process.
4 is an example of a method of manufacturing a fine metal pattern by an inkjet or printing process.
5 is an example of a method of manufacturing a fine metal pattern having a high aspect ratio by an MSAP process.
6 is a simplified cross-sectional view of a fine metal pattern formed on an overcoat layer of a quantum dot-based color conversion film.
7 is a simple cross-sectional view of a fine metal pattern formed on one or both surfaces of a retardation film.
8 is a simple cross-sectional view of a fine metal pattern formed on one or both surfaces of a polarizing film.
9 is a simplified cross-sectional view of a fine metal pattern formed on an encapsulation layer of an OLED.
10 is an example comparing the surface roughness of a polyimide film having surface defects after planarization with a functional organic layer.
11 is a TEM image of silver nano catalyst particles formed in a matrix after hard baking.
12 is an optical micrograph of a primer pattern formed on a substrate.
13 is an SEM photograph and XRD data of a copper layer formed after a plating process.
14 is a result of forming a first metal layer by electroless plating after photoresist development.
15 is an optical micrograph, SEM analysis, and elemental mapping results of a microelectrode grid pattern prepared according to the manufacturing method.

Hereinafter, the present invention will be described in detail.

The present invention relates to the production of conductive metal layers or fine metal patterns that can be used in electrode systems, optical sensors and conductive films, printed circuits and semiconductor packaging substrates of various electronic devices, and conductive laminates formed on one or both sides on any substrate or The conductive micropattern lamination is made of (i) a functional undercoat, (ii) a primer layer, (iii) at least one metal selected from iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, or an alloy thereof. It is characterized in that it is composed of a three-layer structure.

The substrate may be glass, metal, ceramic, three-dimensional plastic molded body and film, etc. generally used in this technical field, and more specifically, the plastic and film have a glass transition temperature of 80 ^o C to 400 ^o C has a range value. 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, It is not limited to this.

It is characterized in that the functional undercoat layer is prepared by a formulation which may further comprise an organic binder, a crosslinking agent, an acid catalyst, an organic solvent and optionally optional fillers.

It is characterized in that the primer layer is prepared by a blend selectively composed of an organic binder, a photopolymerizable binder, a crosslinking agent, a metal ion organic complex, a photoinitiator or a photoacid generator, an organic solvent and a filler selected by necessity.

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, polyvinylphenols such as poly(4-vinylphenol) or alkylated melamine resins 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 a hydrogen atom, an oxygen atom, a nitrogen atom, a fluorine atom, a 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 by 1 type 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 undercoat 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, and the like, and may 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 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, fillers may be included as needed for the purpose of improving adhesive strength, electrical properties, minimum dielectric loss, and heat dissipation characteristics. 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 by way of example 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-hepta Fluoro-7,7-dimethyl-4,6-octanedione natosilver (I) complex, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dionenay Tosilver (I) complex, 1,1,1,5,5,5-hexafluoropentane-2,4-dionenatosilver (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-Dionenatosilver(I) complex, 1,1,5,5-tetrafluoropentane-2,4-dionenatosilver(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-trifluoroacetoacetate Tosilver(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-pentaflu Or-3-oxopentanonatosilver(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, 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 functional undercoat formulation and primer 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.

In addition, other additives may be included, if necessary, for the purpose of removing residual ions in the cleaning solution composition after development. The other additives are generally known in the art and include, but are not limited to, for example, anionic surfactants, cationic surfactants, amino acids, 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 strong alkaline aqueous solution may be used for surface treatment of the substrate in a wet method, but sodium hydroxide, potassium hydroxide, etc. may be mentioned as specific examples of the alkali agent, but not limited thereto, and may be used in a concentration of 0.1 to 2 molarity. have.

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 functional undercoat formulation and the primer formulation may be applied by a wet thin film coating method, and are 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; spray coating method; inkjet method; pen lithography such as fountain pen nanolithography (FPN) and dip pen nanolithography (DPN); embossing printing methods such as letterpress printing, flexographic printing, resin embossing printing, contact printing, microcontact printing (μCP), nanoimprinting lithography (NIL), and nanotransfer printing (nTP); intaglio printing methods such as gravure printing and engraving; lithography; stencil printing methods such as screen printing and copying; It is applied by an offset printing method or the like, 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 fine patterned primer layer formed on the substrate obtained as described above, a metal seed layer is formed on the primer layer, and if necessary, electroless or electrolytic plating is performed. Mixing is carried out and the metal layer is further grown. The electroless or electrolytic plating treatment (process) is not particularly limited, and can be performed by any generally known plating treatment (process). For example, using a conventionally generally known plating solution, the plating solution (bath) Immersion method 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.

The electrolytic plating solution mainly contains copper sulfate, and may further include various additives according to other uses.

Here, the metal plating film formed by electroless or mixed electrolytic plating includes 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

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.

Table 2 below shows that after the flexible copper foil samples were prepared with the selected functional undercoat and photosensitive primer formulation, peel strength was measured and confirmed by a push-pull gauge.

As shown in Tables 1 and 2, in the plating films (Examples 1 and 2) formed using the functional undercoat and photosensitive primer layer of the present invention, excellent adhesion on the adhesive surface was obtained even with polyimide having surface defects. Confirmed.

Claims (17)

A fine metal pattern formed on one or both surfaces of an arbitrary substrate, wherein at least one selected from (i) a functional undercoat, (ii) a primer, (iii) iron, cobalt, nickel, copper, palladium, silver, tin, platinum, and gold A fine metal pattern having a three-layer structure composed of metals or alloys thereof.
The method of claim 1,
The functional undercoat and primer are a polymeric resin layer that can be prepared by a photopolymerizable binder, an organic binder that can be thermally cured or crosslinked.
According to claim 2, wherein the organic binder resin is polyethyleneimine, urea resin, phenol resin, alkylated melamine resin, polyurethane, polyamic acid, polyimide, polyvinyl alcohol, polyvinyl phenol, (hydroxypropyl) methyl cellulose, hype Resin prepared by polyfunctional monomer having hypromellose, hypromellose phthalate, polysaccharides, aziridine or glycidyl group, polyfunctional monomer having unsaturated ethylene group, or It is a resin prepared by an oligomer, or a copolymer resin prepared including a carboxyl group monomer, and at least one or more selected from a copolymer resin prepared including a maleimide monomer, or a combination thereof, characterized in that fine metal pattern.
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 fine metal pattern selected from one or a combination of ethylene urea-formaldehyde resins, characterized in that it is 1 to 50 weight percent of the total solids content of the formulation.
According to claim 1 or 2, 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, carbide At least one selected from silicon, barium sulfate, mica powder, silica powder, talc powder, carbon nanotubes, boron nitride nanoparticles, graphite, carbon black, flame retardant, and kaolin, and 0.5 to 80 weight percent of the total solid content of the formulation Characterized by a fine metal pattern.
The method according to claim 1 or 2, wherein the functional undercoat and primer may further contain an organic metal ion complex if necessary, and is preferably 0.0005 to 20 parts by weight based on 100 parts by weight of the total organic solid content of the total formulation. Preferably, the fine metal pattern comprising 0.01 to 5 parts by weight or less.
A method for manufacturing a fine metal pattern based on a photolithography process, comprising:
First step: forming a functional undercoat on any substrate;
Second step: applying a primer on the undercoat;
Third step: placing a mask on the primer and irradiating it with light having a wavelength of 360 nm or more, then baking at 80 ^o C to 170 ^o C conditions;
Step 4: Developing and cleaning the unexposed portion of the primer;
Step 5: Forming catalyst particles in-situ inside the primer at 50 ^o C to 200 ^o C conditions;
Step 6: forming a first metal layer by electroless plating on the primer; and
7th step; A method of manufacturing a fine metal pattern comprising forming a second metal layer by an electrolytic plating process.
As a method for manufacturing a fine metal pattern based on a printing or inkjet process,
First step: forming a functional undercoat on any substrate;
Second step: selective application of primer by inkjet or printing equipment;
Third step: after irradiation with light having a wavelength of 360 nm or more, forming in-situ catalyst particles inside the primer at 50 ^o C to 200 ^o C conditions;
Step 4: forming a first metal layer by electroless plating on the primer; and
5th step; A method for manufacturing a fine metal pattern comprising the step of forming a second metal layer by an electrolytic plating method.
A method for manufacturing a fine metal pattern having a high-aspect ratio by a modified semi-additive process (MSAP) process based on a non-etching method using a functional undercoat and a primer, comprising:
Step 1: After applying a functional undercoat on an arbitrary substrate, heat treatment at UV or 50 ^o C to 300 ^o C conditions;
Second step: forming a primer on the undercoat;
Third step: heat-treating the primer under UV light or 50 ^o C to 200 ^o C conditions;
Step 4: forming a photoresist layer on the primer;
Step 5: Developing after selective exposure with light of 365 nm or more under masking;
Step 6: Forming a first metal layer on the exposed portion by an electroless plating method;
Step 7: Forming a second metal layer on the first metal layer formed by an electrolytic plating method; and
Step 8: Finally removing the photoresist
A method of manufacturing a fine metal pattern comprising a.
10. The method of claim 9, wherein the method comprises a step of using a primer excluding the functional undercoat alone or using a functional undercoat excluding the primer alone.
10. The method according to any one of claims 7 to 9, wherein the thickness of the first metal layer is 0.05 um to 10 um, preferably 0.1 um to 2 um.
[10] The method according to any one of claims 7 to 9, wherein a pitch of the fine metal pattern is 1 um to 500 um.
[Claim 7] The microstructure according to any one of claims 1 to 6, wherein the optional substrate is glass, metal, ceramic, a three-dimensional plastic molded article having a glass transition temperature of 80 ^o C to 400 ^o C, and a film. metal pattern.
The method according to any one of claims 1 to 6, wherein the optional substrate is a polarizing film, a retardation film, an overcoat layer of a color filter, an overcoat layer of a color conversion film, A fine metal pattern, characterized in that it further comprises an encapsulation layer (encapsulation) of the OLED and forms a fine metal pattern on one side or both sides.
According to claim 1, wherein the functional undercoat and primer is a printed circuit board, a chip on film (Chip on film), build-up (build-up) printed circuit board, fine copper wire or redistribution layer of a semiconductor packaging substrate (Redistribution layer) ) fine metal pattern, characterized in that it can be used for manufacturing.
The conductive wiring (Electrode), the anode (Cathode), the cathode (Andode), the source/drain according to claim 1, wherein the functional undercoat and the primer constitute a display, an optical sensor, a photonic device, a solar system or a flexible electronic device. (Source/drain) electrode, a fine metal pattern, characterized in that it can be used to manufacture the gate (Gate) electrode.
The method according to claim 1, wherein the functional undercoat and primer can be used for manufacturing a metal mesh or metal grid electrode, and a digitizer, a pressure sensor electrode, a touch sensor electrode, a wireless communication antenna ( Antenna) electrode, a transparent heater, a fine metal pattern, characterized in that it can be used in the manufacture of a 3D negative plate of a secondary battery.

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