KR100958289B1 - Resin composition containing catalyst precursor for electro-magnetic sheilding, forming method of metallic pattern using the same and metallic pattern prepared thereby - Google Patents

Abstract

The present invention relates to a catalyst precursor resin composition for shielding electromagnetic waves, a method of forming a metal pattern using the same, and a component or device including the metal pattern and the metal pattern formed accordingly. According to the present invention, a catalyst precursor for forming a metal pattern comprising a copolymer resin having a carboxylic acid functional group and a cardo functional group, a fluorinated silver ion organic complex precursor, a monomer having a polyfunctional ethylenically unsaturated bond, a photoinitiator and an organic solvent A resin composition is provided, and a method of forming a metal pattern using the same to form a catalyst precursor pattern, reducing the electroless plating and then electroless plating, and a component or device including the metal pattern and the metal pattern thus formed are provided. . By forming a metal pattern using the catalyst precursor resin composition of the present invention, the adhesion of the formed catalyst film is excellent, there is little catalyst loss during the wetting process such as development or plating process, and the deposition rate is improved to be uniform after electroless plating. A fine metal pattern is formed. The metal pattern manufacturing method of the present invention can be used to form wiring of an electromagnetic shielding film or a flexible circuit board generated from the front surface of a display such as CRT, PDP, liquid crystal, or EL.

Electromagnetic shielding, metal fine pattern formation, fluorinated silver ion organic complex, chemical resistant copolymer, copolymer resin including carboxylic acid functional group and cardo functional group

Description

FIELD OF THE INVENTION A catalyst precursor resin composition for shielding electromagnetic waves, a method of forming a metal pattern using the same, and a metal pattern formed according to the present invention.

The present invention relates to a catalyst precursor resin composition used to form a metal pattern, a method of forming a metal pattern using the same, and a metal pattern and a component and a device including the metal pattern formed accordingly. More specifically, a catalyst precursor resin composition for electromagnetic wave shielding comprising a copolymer resin having a cardo functional group and a carboxylic acid functional group used to form a metal pattern for electromagnetic wave shielding and a fluorinated silver ion organic complex, and forming a metal pattern using the same The present invention relates to a method, a metal pattern formed thereby, and a component and a device including the metal pattern.

Recently, as various types of displays have been commercialized, the harmful effects of the human body and the malfunction of the devices due to electromagnetic interference (EMI) generated from such displays have emerged as major problems. In order to solve this problem, a conductive shielding film is formed on the front of the display to distort the traveling direction of the electromagnetic wave, and then grounded and emitted.

As a method of shielding electromagnetic noise generated from the front surface of a display such as a CRT or PDP, a method of depositing a metal or metal oxide on a transparent substrate and forming a thin conductive film is known. However, such a method requires that a thin film be deposited to provide transparency. In this case, sufficient electric wave shielding effect cannot be obtained because the surface resistance of the conductive layer becomes too large.

The most commonly used method is metal foil etching, in which copper foil is adhered on a transparent substrate and subjected to an exposure process to obtain a photoresist pattern, and copper foil is formed by etching copper foil. However, this method is not affinity, because the process is long and complex, and a large amount of metal waste is generated. In addition, the intersection of the copper pattern in the process is inevitable problem.

In addition to the above method, it has been reported to form the electromagnetic shielding film by patterning the conductive paste by electroless or plating treatment by printing method such as screen printing and offset printing, but in this case, there is a limit to the precision of the printed circuit, There is a problem that conductive materials seep into the uneven portion.

In addition, a method of forming a metal layer and plating or electroless plating by a photo developing method has been proposed. However, the photo developing method requires several layers and has a complicated process. On the other hand, it has been reported that after the metal catalyst is mixed with the photosensitive resin and developed, electroless plating and electroplating are performed. Such a method has excellent pattern characteristics and can form fine patterns. The solution to the problems associated with electroless plating, such as pattern desorption in a strong base aqueous solution, is not specifically presented.

Accordingly, the present inventors have found that the above problems can be solved by using a composition containing a specific catalyst precursor and a specific resin as a result of many studies to solve the problems of the prior art.

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst precursor resin composition having excellent pattern characteristics, capable of forming a fine pattern, less loss of catalyst during wet processes such as development and electroless plating, and excellent chemical resistance, adhesion, and deposition resistance. To provide.

Another object of the present invention is to provide a method of forming a metal pattern using the catalyst precursor resin composition.

Another object of the present invention is to provide a metal pattern formed by the method of the present invention.

Furthermore, another object of the present invention is to provide a component, an element, an electromagnetic shielding material or a flexible circuit board comprising a metal pattern formed by the method of the present invention.

According to one aspect of the invention,

(a) a copolymer resin having a carboxylic acid functional group and a cardo functional group,

(b) fluorinated silver ion organic complex precursors,

(c) a monomer having a polyfunctional ethylenically unsaturated bond,

(d) photoinitiators, and

(e) The catalyst precursor resin composition for metal pattern formation containing an organic solvent is provided.

According to another aspect of the present invention,

(a) forming a catalyst precursor pattern on a substrate using the catalyst precursor resin composition according to the present invention;

(b) reducing the formed catalyst precursor pattern to form a catalyst pattern; And

(C) there is provided a metal pattern forming method comprising the step of electroless plating on the catalyst pattern.

According to another aspect of the present invention,

A metal pattern formed by the method according to the present invention is provided.

Furthermore, according to another aspect of the present invention,

A component, an element, an electromagnetic wave shield, or a flexible circuit board including a metal pattern formed by the method according to the present invention is provided.

By forming a metal pattern using the catalyst precursor resin composition of the present invention, the adhesion of the formed catalyst film is excellent, there is little catalyst loss during the wetting process such as development or plating process, and the deposition rate is improved to be uniform after electroless plating. A fine metal pattern is formed. The metal pattern manufacturing method of the present invention can be used to form wirings of electromagnetic shielding films (shielding materials) or flexible circuit boards generated from the front surface of displays such as CRT, PDP, liquid crystal, and EL.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention have studied a method for forming a metal wiring with a simple process, a fine metal pattern, and excellent pattern characteristics. As a result, a copolymer polymer resin and a fluorinated silver ion complex containing a carboxylic acid functional group and a cardo functional group have been studied. By using the catalyst precursor resin composition comprising a chemical resistance, adhesion, deposition, storage and stability in the catalyst precursor resin composition and metal pattern formation process was found to be improved. That is, the catalyst precursor resin composition of the present invention is excellent in chemical resistance and can obtain a stable pattern even in wet processes such as electroless plating using strong bases, and excellent adhesion of the formed catalyst layer, and wetness such as development or plating process. Less catalyst loss during the process improves the deposition rate, and the catalyst precursor has excellent compatibility with the organic solvent and the resin so that precipitation does not occur, and thus the stability is excellent, thus showing excellent patternability and electroless plating. As a result, a uniform fine metal pattern is formed.

In one embodiment of the present invention, (a) a copolymer resin containing a carboxylic acid functional group and a cardo functional group, (b) a fluorinated silver ion organic complex precursor, (c) a monomer having a polyfunctional ethylenically unsaturated bond A catalyst precursor resin composition comprising (d) a photoinitiator and (e) an organic solvent is provided.

Organic polymer resin constituting the catalyst precursor resin composition of the present invention, that is, Copolymer resin In order to minimize chemical resistance and loss of the catalyst precursor, a copolymer resin having a carboxylic acid functional group and a cardo functional group is used.

The copolymer resin having a carboxylic acid functional group and a cardo functional group may be synthesized by a reaction of a dialcohol and / or a diamine having a cado functional group and a diacid anhydride. Alcohols or amines in the dialcohol or diamine having a Cado functional group act as functional groups for the polymerization. Examples of dialcohols and diamines having a Cado functional group include, but are not limited to, compounds of the following formula (1). The dialcohol and diamine monomer having a cardo functional group of Formula 1 may be used alone or in combination of two or more. In general, as the monomer, any compound having an amine group or an alcohol group introduced through an ether or ester bond with an alcohol of phenol of 9,9-bis (4-hydroxyphenyl) florin may be used.

[Formula 1]

The copolymer resin used in the catalyst precursor resin composition of the present invention must also have a carboxylic acid functional group to impart solubility to the basic aqueous solution (developer). As described above, the carboxylic acid group is reacted with a dialcohol or a diamine having a cado functional group to form an amide bond or an ester bond and an acid is formed, thereby forming a carboxylic acid group in the copolymer resin. Is introduced. The mechanism in which a copolymer having a cardo functional group and a carboxylic acid functional group is formed by the reaction of the acid anhydride and a dialcohol having a cardo functional group or a diamine is shown in Schemes 1 and 2 below.

Scheme 1

Scheme 2

Diacid anhydrides may be used as the acid anhydride. As the acid anhydride, various diacid anhydrides may be used according to R 2 in the acid anhydride formulas of Schemes 1 and 2, but examples of the diacid anhydride that may be generally used are the following Chemical Formula 2 Same as These diacid anhydrides may be used alone or in combination of two or more. In terms of chemical resistance and reactivity, preferably those having a diphthalic anhydride functional group can be used.

[Formula 2]

In addition, when synthesizing the copolymer resin, other monomers besides the dialcohol and the dialcohol or diamine monomer having a cardo functional group may also be further included. Preferably, a dialcohol or a diamine having an aromatic functional group may be used as the other monomer in consideration of the adsorptivity and chemical resistance with the substrate.

In the copolymer resin having a carboxylic acid functional group and a cardo functional group, a dialcohol and / or a diamine having a cardo functional group may be used in an amount of 110 to 150 moles, preferably 130 to 140 moles based on 100 moles (mol%) of a dihydrate. Can be. If the dialcohol and / or the diamine having a cardo functional group is less than 110 moles with respect to 100 moles of the diacid anhydride, the amount of the diacid anhydride monomer remaining at the end of the polymerization increases, and if it exceeds 150 moles, the residual diacid anhydride at the end of the polymerization Increasing amounts of dialcohols and / or diamines and poor storage stability due to their interaction with the silver fluoride organic complex precursor.

The copolymer resin may have a weight average molecular weight of 2,000 to 15,000, preferably 4,000 to 8,000. If the weight average molecular weight of the copolymer resin is less than 2,000, the curing property is poor, so that the adhesive property is deteriorated and the shape of the micropattern is not good. If the molecular weight is more than 15,000, the solubility of the developer is increased and the quality of the pattern thin film is deteriorated.

The copolymer resin is preferably an acid value of 90 ~ 300mg KOH / g, preferably 150 ~ 250mg KOH / g to be used for fine pattern formation using a catalyst. If the acid value of the copolymer resin is less than 90mgKOH / g, the solubility of the coating thin film in the alkaline developer is low, the phenomenon is likely to be poor, and if the acid value exceeds 300mgKOH / g, solubility is too high, pattern defects such as disconnection or separation It is easy to occur.

The carboxylic acid functional group and the cardo functional group Since the copolymer resin having excellent compatibility with the silver fluoride complex, the catalyst precursor resin composition containing the copolymer resin and the silver fluoride complex exhibits excellent storage and stability. Since the copolymer resin is also excellent in developability, pattern characteristics, and chemical resistance, the shape of the pattern is uniformly and excellently formed even in a strong base state such as a formalin copper plating bath. Since this is minimized, the stability of the pattern formed from the catalyst precursor resin composition of the present invention is also excellent.

Catalysts constituting the catalyst precursor resin composition of the present invention include catalyst stability, miscibility with organic solvents, pattern loss, catalyst loss in wet processes such as development and electroless plating, adhesion characteristics, electroless plating characteristics, and In terms of manufacturing cost, fluorinated silver ion organic complexes are used.

In the case of using silver particles as a catalyst, it is difficult to uniformly disperse the catalyst in the composition, and since the aggregation is likely to occur, a stabilizer such as a surfactant should be added to the composition. In addition, when the silver particles are used in an excessive amount, developability is reduced, making it difficult to form a fine catalyst pattern layer, and adhesion properties may be reduced.

The inorganic silver salt may be dissolved in an aqueous solution and may be lost during development or electroless plating, and may have poor compatibility with an organic solvent and a resin, deposition characteristics of an electroless plating, and adhesion characteristics of a catalyst pattern layer.

Since the silver ion organic complex has insufficient compatibility with the organic solvent, the stability of the composition for forming the catalyst pattern may be deteriorated. Therefore, when the catalyst pattern is formed, the silver ion organic complex is not uniformly coated but formed as a uniform fine catalyst pattern. There is a difficult problem. Therefore, in the catalyst precursor resin composition of the present invention, a fluorinated silver ionic organic complex having excellent stability, adhesion, and deposition property is used as the catalyst precursor material.

In addition, since the silver fluoride ion complex is more compatible with the organic solvent, the catalyst precursor resin composition is stable, has a very good catalyst-like pattern, and has low solubility in water. This does not seem to happen well. In addition, since the adsorption power of the catalyst precursor and the substrate in the resin composition is increased in the electroless plating solution which is a basic aqueous solution, a uniform and excellent deposition film can be obtained.

The fluorinated silver ion organic complex which can be used in the resin composition of the present invention is not limited thereto, but is largely silver fluoride acetate, fluorinated silver sulfonate, fluorinated β-carbonyl ketone silver (I A) complexes and fluorinated β-carbonyl ester-based silver (I) complexes, and one or two or more kinds of fluorinated silver ion organic complexes selected therefrom may be used together.

Specifically, silver (I) fluorosulfate, silver (I) trifluoroacetate, silver (I) trifluoromethane sulfate, silver (I) pentafluoropropionate, silver (I) heptafluorobutyrate, etc. are mentioned.

Examples of such fluorinated silver ion organic complexes include, but are not limited to, 1,5-cyclooctadiene-hexafluoroacetylacetonatosilver (I) complexes, 1,1,1-trifluoro-2, 4-pentanedionenatosilver (I) complex, 5,5-dimethyl-1,1,1-trifluoro-2,4-hexanedionenetosilver (I) complex, 1- (4- Methoxyphenyl) -4,4,4-trifluorobutanedionenetosilver (I) complexes, 5,5,6,6,7,7,8,8,9,9,10,10,11 , 11,12,12,12-heptadecafluordecane-2,4-dionenatosilver (I) complex 1,1,1,2,2,3,3-heptafluoro-7,7-di Methyl-4,6-octanedionenetosilver (I) complex, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dionenetosilver (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-dione-natosilver (I) complex, 5H, 5H-perfluorononane-4,6-dione-natosilver (I) complex, 6H, 6H-perflu Le-Undecan-5,7-dione-natosilver (I) complex, 8H, 8H-perfluoropentadecan-7,8-dione-natosilver (I) complex, 6H, 6H-perfluor Undecane-5,7-dionenetosilver (I) complex, 1-phenyl-2H, 2H-perfluorohexane-1,3-dionenetosilver (I) complex, 1-phenyl-2H , 2H-perfluoro decane-1,3-dionenatosilver (I) complex, 5,6,6,6-tetrafluoro-5- (heptafluoropropoxy) hexane-2,4-dione Neatosilver (I) complexes, 1,1,5,5-tetrafluoropentane-2,4 dioneneatosilver (I) complexes, 5,5,6,6,7,7,8,8 , 9,9,9-Undecanefluoro-nonane-2,4-dionenatosilver (I) complex, ethyl 3-chloro-4,4,4-trifluoroacetoacetotosilver (I) complex Water, ethyl-4,4-difluoroacetoacetotosilver (I) complex, ethyl-4,4,4-trifluoroacetoacetotosilver (I) complex, isopropyl-4,4,4 Trifluoroacetoacetotosilver (I) complexes, methyl-4,4,5,5,5-pentaplu Le-3-oxopentanonate silver (I) complexes, ethyl-4,4,5,5,5-pentafluoro-3-oxo-pentanonate silver (I) complexes and 1,1,1, And 5,5,6,6,6-octafluoro-2,4-hexanedionetosilver (I) complexes. The fluorinated silver ion complexes may be used alone or in combination of two or more.

In the catalyst precursor resin composition of the present invention, the fluorinated silver ion organic complex may be used in an amount of 2 to 40 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total organic solids. In the resin composition of the present invention, if the content of the silver fluoride ion complex is less than 2 parts by weight, the amount of the catalyst is not sufficient, and the deposition rate of the metal is significantly slowed during electroless plating, and a uniform metal thin film is formed on the catalyst pattern. It's hard to be. On the other hand, when the amount of the silver fluoride ion complex is more than 40 parts by weight, the storage properties of the composition, the developability of the catalyst pattern, and the adhesion properties are reduced, making it difficult to form a uniform fine catalyst pattern, and also forming a fine metal thin film on the catalyst pattern. It becomes difficult to form. The term 'total organic solids' refers to any organic solids in the catalyst precursor resin composition including an organic polymer resin, a silver ion organic complex precursor, and other organic substances added as required in the catalyst precursor resin composition of the present invention. it means.

The monomer having a polyfunctional ethylenically unsaturated bond constituting the catalyst precursor resin composition of the present invention is used to promote photocuring and improve developability, and to improve adhesion, chemical resistance, etc. of the catalyst forming film during electroless plating.

Examples of the monomer having a polyfunctional ethylenically unsaturated bond include, but are not limited to, 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, and the number of propylene groups 2-14 propylene glycol diacrylate or propylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate A compound of a polyhydric alcohol and an α, β- unsaturated carboxylic acid obtained by esterification; Compounds obtained by adding acrylic acid or methacryl to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a polyhydric carboxylic acid with a compound having a hydroxyl group or an ethylenically unsaturated bond such as phthalic acid ester of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate; and adducts with multi-polyisocyanates such as compounds having hydroxyl groups or ethylenically unsaturated bonds, such as toluene diisocyanate adducts of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate. . The monomer having the multi-functional ethylenically unsaturated bond may be used alone or in mixture of two or more thereof.

The polyfunctional ethylenically unsaturated bond-containing monomer is preferably two or more functional groups having an ethylenically unsaturated bond in terms of the shape of the fine catalyst pattern and chemical resistance and adhesion during electroless plating.

The content of the multifunctional ethylenically unsaturated bond-containing monomer may be 20 to 150 parts by weight based on 100 parts by weight of the copolymer resin. If the content of the monomer having a polyfunctional ethylenically unsaturated bond is less than 20 parts by weight, it is not sufficiently cured, and it is difficult to form a fine pattern by a catalyst and defects such as dissolution and peeling may occur during electroless plating, and more than 150 parts by weight. In this case, it is difficult to form a fine catalyst pattern because the coating property is reduced and not uniformly cured to the inside.

Photoinitiators constituting the catalyst precursor resin composition of the present invention can be used that is generally known to be usable in the art, it is not particularly limited to the kind, for example, acetophenones, benzophenones, US At least one kind of photoinitiator selected from the group consisting of Hiler benzoylbenzoate, α-amyloxime ester, thioxanthones and triazines can be used.

Examples of acetophenones include, but are not limited to, 2-benzyl-2 (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone) ((2-Benzyl-2 ( dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, IRGACURE 369), α, α-dimethoxy-α-phenylacetophenone (α, α-dimethoxy-α-phenylacetopheone, IRGACURE 651) , IRGACURE 1300 (IRGACURE 369 (30 wt%) + IRGACURE 651 (70 wt%)), 1-benzoylcyclo-hexanol (1-Benzoylcyclohexanol, IRGACURE 184), 2,2'-dimethoxy-2-phenyl-acetophenone ( 2,2'-Dimethoxy-2-phenyl-acetophenone (DMPA), 2,2-diethoxyacetophenone (DEAP), 4-methylmercapto-α, α-dimethyl-morpholino aceto It may include phenone (4-Methylmercapto-α, α-dimethyl-morpholino acetophenone).

Examples of the benzophenones include, but are not limited to, 1-phenyl-1,2-propanedione-2-0-benzoyloxime (1-Phenyl-1,2-Propanedione-2-O-benzoyloxime, PPO), eta Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-O-acetyloxime (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl ) -9H-carbazol-3-yl] -1- (O-acetyloxime) (CGI242).

The thioxanthones may include, but are not limited to, 2-chlorothio-xanthane and 2-isopropylthioxanthane.

The triazines may include, but are not limited to, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid (TPA).

The photoinitiator may be used in 1 to 25 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the copolymer resin. If the content of the photoinitiator is less than 1 part by weight, the catalyst pattern layer is not formed, which is not preferable. If the content is more than 25 parts by weight, the accuracy of the pattern is lowered.

In addition, if necessary, the photosensitizer may be used in the resin composition of the present invention in an amount of 10 parts by weight or less, preferably 0.1-10 parts by weight, based on 100 parts by weight of the mixture of the copolymer resin and the photoinitiator. If the photosensitizer content exceeds 10 parts by weight, the accuracy of the pattern is lowered, which is not preferable.

Photosensitizers may also be used, which are generally known to be usable in the art, and are not particularly limited in their kind, for example n-butylamine, triethylamine and tri-n-butylphosphine At least one kind of photosensitizer selected from the group consisting of can be used.

Although the solvent which comprises the catalyst precursor resin composition of this invention is not specifically limited, For example, Alcohol, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and n-methyl-2-pyrrolidone; Aromatic hydrocarbons such as toluene, xylene and 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, dipropylene glycol ethyl ether; Acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol ethyl ether acetate; At least one selected from the group consisting of N, N-dimethylacetamide, N, N-dimethylformamide, amides such as acetonitrile and the like can be used.

Further, the catalyst precursor resin composition of the present invention is not limited thereto, but may further include additives such as a wetting agent, an adhesion promoter, and the like, which can be generally used as needed in the art when preparing a catalyst precursor resin composition. Can be.

The mixing ratio of the solvent and the organic polymer resin, the fluorinated silver ion organic complex precursor and other additives in the catalyst precursor resin composition of the present invention is not particularly limited, and the substrate is coated with the precursor resin composition and then the solvent is dried. In order to form an efficient and excellent catalyst layer can be suitably mixed in a general mixing ratio known in the art, it does not particularly limit the solid content of the catalyst precursor resin composition, the solid content of the catalyst precursor resin composition The content may preferably be 10-50% by weight. If the solids content exceeds 50% by weight, the viscosity is not high uniformly coated, if the solids content is less than 10% by weight, it is not preferable because the thickness becomes thinner to decrease the mechanical strength of the thin film.

In another embodiment of the present invention, a metal pattern forming method using the metal catalyst precursor resin composition according to the present invention is provided. According to the present invention, the metal pattern is formed on the substrate by using the metal catalyst precursor resin composition of the present invention to form a pattern to form a catalyst precursor layer, reducing the catalyst and then electroless plating the metal pattern.

In the present invention, it is preferable to use a transparent substrate in order to prepare a transparent electromagnetic shielding material, and specifically, but not limited thereto, glass, polycarbonate, acrylic resin, PET, tri acetyl cellulose (TAC), poly Plastic sheets or plastic films such as vinyl chloride resin, polyamide resin, polyimide resin, epoxy resin, and the like can be used. The thickness of the other substrate and the like are general in the art and are not particularly limited.

The catalyst film pattern is formed in the said base material using the catalyst precursor resin composition which concerns on this invention. As the catalyst pattern, a pattern forming method (photolithography method) by exposure and development, offset printing, inkjet printing, imprint or screen printing, or the like may be used. It is more preferable to form a pattern by the pattern formation method (photolithography method) by exposure and image development formed by the very excellent fine metal pattern.

When the pattern is formed by exposure and development in the method of forming a pattern (photolithography method), first, the resin composition of the present invention is applied to the substrate to form a metal catalyst precursor resin film. The coating method is not particularly limited and may vary depending on the characteristics of the coating liquid or the coating amount. Although application | coating is not limited to this, For example, it can carry out by conventional coating methods, such as roll coating, gravure coating, dip coating, bar coating, spray coating, or spin coating.

Thereafter, the coated metal catalyst precursor resin film is exposed and developed to form a catalyst precursor pattern. The exposure and development steps can be carried out by generally known methods. For example, in the exposure process, a mask having an exposure pattern can be used for exposure in a contact or non-contact exposure method. As the light source in the exposure process, a conventional light source such as a halogen lamp, a high pressure mercury lamp, or a metal halide lamp may be used. The development can be performed using a spray method or a dipping method.

The catalyst precursor pattern formation may also be formed by the method of offset printing, inkjet printing, imprint or screen printing as described above. Although the formed catalyst precursor film pattern is not limited to this, It is preferable that the width | variety of a line is 30 micrometers or less, Preferably it is 20 micrometers or less. In addition, the catalyst precursor resin composition of the present invention is sufficiently applicable to fine pattern formation of 10 μm or less. After the exposure and development processes, it is appropriate that the ratio (opening ratio) of the space without a pattern is 60% or more, more preferably 70% or more.

After forming the catalyst precursor pattern as described above, to improve the electroless plating property, the fluorinated silver ion organic complex precursor is reduced to become the catalyst pattern. The silver fluoride ion organic complex precursor may be spontaneously reduced by the electroless plating solution during electroless plating, depending on the type, but the reduction by the electroless plating solution is not sufficient, and in this case, the silver fluoride ion There is a need for a reduction process of an organic complex precursor.

The reduction of the silver fluoride ion complex complex precursor may be carried out by any method generally applicable in the art, and is not limited thereto, for example, by using a reducing agent or by reducing heat and / or UV exposure. can do. In the case of using a reducing agent, any reducing agent generally known in the art may be used, but is not limited thereto. For example, an aqueous solution of sodium borane hydride (NaBH ₄ ) or ascorbic acid may be used. Can be.

It is preferable to use a reducing agent aqueous solution having a concentration of about 0.01-1.0 M. When the concentration of the reducing agent solution is less than 0.01M, the reducing power is not sufficient, and the silver ion organic complex is not sufficiently reduced. When the concentration of the reducing agent is more than 1.0M, it is difficult to control the degree of reduction and the catalyst pattern film may be damaged. The reducing agent aqueous solution may be applied by spray or dipping.

UV exposure or reduction using heat is not a wet process and is preferable in terms of preventing the loss of the catalyst. Particularly, in the case of the silver fluoride ion complex according to the present invention, the catalyst is activated by UV exposure. Reduction is more preferred.

In the formation of the catalyst pattern layer, if necessary, after coating of the catalyst precursor resin composition, it may be post-heat curing after exposure and / or development after exposure, and such a process is common in the art, and may be performed as necessary. The present invention does not limit the present invention.

As described above, after the catalyst precursor pattern layer is formed on the substrate using the catalyst precursor resin composition according to the present invention, the catalyst precursor is reduced with the catalyst, and the metal pattern is formed by electroless plating on the catalyst pattern. The electroless plating is not particularly limited and may be performed by any electroless plating method generally known in the art. In the present invention, copper plating or silver plating can be performed, and copper plating is preferable in view of cost and electromagnetic shielding performance.

Electroless copper plating may be carried out using, for example, a plating liquid which is generally known in the art, and is not limited thereto, for example, metal ion salts such as copper sulfate, reducing agents such as formalin, complexing agents such as EDTA, and traces of other It can carry out using the well-known plating liquid containing an additive.

The total thickness of the catalyst pattern layer and the metal layer in the final electromagnetic shielding film including the metal pattern formed by the method according to the present invention can be controlled by the metal salt or metal ion concentration of the plating bath, plating temperature, deposition time and the like.

The thickness of the catalyst pattern layer and / or the metal layer may vary depending on the width of the pattern, and the person skilled in the art may adjust the thickness of the catalyst pattern layer and / or the metal layer to have a suitable thickness as necessary. Although not necessarily, the total thickness of the catalyst pattern layer and the metal layer may be 0.3 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 1-8 μm. When the total thickness of the catalyst pattern layer and the metal layer is less than 0.3 μm, the mechanical strength is not sufficient and the conductivity is not sufficient, so that the shielding property may be lowered. If the total thickness of the catalyst pattern layer and the metal layer exceeds 8 mu m, the thickness becomes so thick that it is not preferable for the post process treatment. In addition, the thickness of the metal layer of the total thickness of the catalyst pattern layer and the metal layer is preferably at least 0.1㎛ (100nm) in consideration of conductivity and electromagnetic shielding.

As such, the metal pattern formed using the catalyst precursor resin composition comprising a copolymer resin having a carboxyl group and a carbohydrate and a fluorinated silver ion organic complex according to the present invention has excellent adhesion of the catalyst pattern layer, There is little catalyst loss during the wetting process, such as the plating process, and the deposition rate is improved to form a uniform and fine metal pattern by electroless plating.

The metal pattern obtained by the method according to the present invention has excellent electromagnetic wave shielding ability, and an electromagnetic wave shielding material generated from the front surface of a display such as a CRT, a PDP, a liquid crystal, an EL, a part or an element including a metal pattern, specifically, a PDP It is suitable for use in forming an EMI film and wiring of a flexible circuit board.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples.

Example 1

A. Organic Polymer Resin (Polymer Resin) Manufacturing

a. Dial alcohol  Monomer Synthesis:

To a 250 mL flask was added 2.0 g (5.708 mmol) 9,9'-bis (4-hydroxyphenyl) proene, 3.155 g (22.83 mmol) potassium carbonate, 50 ml 2-butanone and stirred at room temperature. 3.173 g (22.83 mmol) 3-bromopropanol was slowly added to the mixture to carry out a substitution reaction. The reaction was stirred at room temperature for 24 hours and then filtered using a filter paper. The filtered solution was extracted using distilled water. In the extraction, an organic solvent (CH ₃ CH ₂ OCH ₂ CH ₃ ) was used. The extracted organic solvent layer was washed with a saturated sodium chloride (NaCl) solution, and water was removed using magnesium sulfate (MgSO ₄ ). And CH ₂ Cl ₂ : CH ₃ OH = purified by column chromatography in a developing solution mixed with a volume ratio of 10: 1 to obtain a white solid monomer (I) with a yield of 78%.

¹ H-NMR (400 MHz, CDCl ₃ ): δ2.013 (m, 4H), 3.837 (t, 4H), 4.076 (t, 4H), 6.752 (d, 4H), 7.120 (d, 4H), 7.265 ( d, 2H), 7.329 (m, 4H), 7.746 (d, 2H)

b . Copolymerization Polymerization:

2.5 g (5.3581 mmol) of the monomer (I) synthesized above, 1.15 g (3.911 mmol) of BPDA (Biphenylphthalic dianhydride), THPA (1,2,3,4-Tetrahydropthalic anhydride) 0.057 g (0.391 mmol), and TBAB in a 100 ml flask 0.02g (Tetrabutylammoniumbromide) and 7.158g of PGMEA (Propylene Glycol Monomethyl Ether Acetate) were added thereto, and the mixture was stirred at 120 ° C for 9 hours. In order to remove residual BPDA, 0.045 g (0.391 mmol) of HEA (Hydroxyethylacrylate) was added to the reaction mixture, and the reaction mixture was heated to 90 ° C. overnight to give an over night reaction to obtain a yellow resin solution. The acid value of the organic polymer resin (solid content 34.4 wt%) thus obtained was 182.64 mgKOH / g and the weight average molecular weight was 3,811.

B. Preparation of Catalyst Precursor Resin Compositions

19.5620 g of the polymer resin solution obtained in A, 12.5006 g of a dipentaerythritol hexa-acrylate (DPHA) solution (50 wt% in PGMEA), 0.8651 g of a photoinitiator IRGACURE 2010 (α-Hydroxyketone), silver trifluoroacetate (AgO ₂ CCF ₃ ) 1.2856 g, KBM 503 (Adhesion promoter) 0.2093 g, 10 wt% BYK 331 (BYK-Chemi) PGMEA solution (Wetting agent solution) 0.2417 g, DMF (N, N- Dimethyformamide) 35.09 g was mixed and stirred at 500 rpm with a stirrer to obtain 70.0000 g of a catalyst precursor resin composition (solid content 22.19 wt%).

C. Form a fine metal pattern

Next, a metal pattern was formed using the catalyst precursor resin composition prepared above in the process as shown in FIG. 1 under the process steps and conditions described below.

(1) Coating: The catalyst precursor resin composition prepared in B was bar-coated to a thickness of 750 nm using a Gap size 10 μm Meyer bar on a 100 μm-thick PET film.

(2) Heat Curing: After bar coating, heat curing was performed at 100 ° C. for 90 seconds.

(3) Exposure: 195 mJ / Cm ² UV light with a wavelength of about 375 nm through a photomask (20 µm mesh pattern) by contact method. Irradiation with energy exposed the catalyst precursor pattern.

(4) Development: ECD-100 (basic aqueous solution of pH 13) of ENF was sprayed onto the exposed catalyst pattern by spraying for 144 seconds, washed with ultrapure water (DI), and developed by blowing nitrogen.

(5) Post-heat curing: After development, post-heat curing was performed at 100 ° C. for 300 seconds.

(6) Reduction: 3.6 J / Cm ² UV in the wavelength region of 330-500 nm is applied to the post-cured catalyst precursor pattern. The energy was irradiated to reduce the catalytic metal.

(7) Copper Electroless Plating: A plating layer having a thickness of 1 μm was formed by performing the ATOTECH Covertron copper plating solution (Copper Bath) at 60 ° C. for 20 minutes.

An optical micrograph of the metal pattern formed by the method of this embodiment is shown in FIG. 2, and the line width of the metal pattern formed in this embodiment was 20 μm.

Example  2

A. Preparation of fat-soluble organic polymer resin

In a 100 ml flask, 2.5 g (5.3581 mmol) of the dialcohol monomer (I) synthesized in Example a, 1.213 g (3.911 mmol) of 4,4'-oxydiphthalicanhydride, THPA (1, 0.057g (0.391mmol) of 2,3,4-Tetrahydropthalic anhydride), 0.02g of TBAB (Tetrabutylammoniumbromide) and 7.158g of PGMEA were added and stirred at 120 ° C for 9 hours. In order to remove residual 4,4'-oxydiphthalic hydride, 0.04 g (0.391 mmol) of HEA (Hydroxyethylacrylate) was added to the reaction mixture, and the reaction mixture was heated to 90 DEG C. to carry out an overnight reaction to obtain a yellow resin solution. . The acid value of the organic polymer resin (solid content 34.4 wt%) thus obtained was 183.21 mgKOH / g and the weight average molecular weight was 4,051.

B. Preparation of Catalyst Precursor Resin Compositions

A catalyst precursor resin composition (solid content 22.19 wt%) was prepared in the same manner as the preparation of the catalyst precursor resin composition of Example 1, except that the organic polymer resin prepared in A of Example 2 was used.

C. Form a fine metal pattern

A catalyst fine metal pattern was formed in the same manner as in the preparation of the fine metal pattern of Example 1, except that the catalyst precursor resin composition prepared in B of Example 2 was used.

Example  3

A. Preparation of fat-soluble organic polymer resin

2.8 g (5.3581 mmol) of diamine monomer of Formula II, 1.15 g (3.911 mmol) of Biphenylphthalic dianhydride (BPDA), THPA (1,2,3,4-Tetrahydropthalic anhydride) 0.057 g (0.391 mmol), TBAB in a 100 ml flask 0.02g (Tetrabutylammoniumbromide) and 7.158g of PGMEA (Propylene Glycol Monomethyl Ether Acetate) were added thereto, and the mixture was stirred at 120 ° C for 9 hours. In order to remove residual BPDA, 0.045 g (0.391 mmol) of HEA (Hydroxyethylacrylate) was added to the reaction mixture, and the reaction mixture was heated to 90 ° C. overnight to give an over night reaction to obtain a yellow resin solution. The acid value of the organic polymer resin (solid content 34.4 wt%) thus obtained was 177.35 mgKOH / g and the weight average molecular weight was 3,651.

B. Preparation of Catalyst Precursor Resin Compositions

A catalyst precursor resin composition (solid content 22.19 wt%) was prepared in the same manner as the preparation of the catalyst precursor resin composition of Example 1, except that the organic polymer resin prepared in A of Example 3 was used.

C. Form a fine metal pattern

A catalyst fine metal pattern was formed in the same manner as in the preparation of the fine metal pattern of Example 1, except that the catalyst precursor resin composition prepared in B of Example 3 was used.

Comparative example  One

A. Preparation of fat-soluble organic polymer resin

12.0 g MMA (Methyl methacrylate), 8.0 g Methyl methacrylic acid (MAA) in a 250 mL flask, 60.33 g mixed solvent of 1: 1 weight ratio of 3-MBA (3-methoxybutyl acetate) and DPM (dipropylene glycol mono methyl ether) After dissolving in, 0.4 g 3-MPA (3-mercaptopropionic acid) was added and stirred. The mixed solution was heated to 60 ° C. under a nitrogen atmosphere and stirred for 1 hour. 0.6 g V-65 (2,2'-azobis-2,4-dimethyl-valeronitrile) was dissolved in 5.0 g of a 1: 1 weight ratio mixed solvent of 3-MBA and DPM, and then added to the mixed solution at 60 ° C. The reaction was carried out at the same temperature for 4 hours. The acid value of the organic polymer resin (solid content 23.17 wt%) thus obtained was 287.74 mgKOH / g and the weight average molecular weight was 8,632.

B. Preparation of Catalyst Precursor Resin Compositions

28.7055 g of the polymer resin solution obtained in A of Comparative Example 1, 12.5006 g of DPHA (dipentaerythritol hexa-acrylate) solution (50 wt% in PGMEA), photoinitiator IRGACURE 2010 (α-Hydroxyketone) 0.8651 g, silver trifluoroacetate (Silvertrifluoroacetate, AgO ₂ CCF ₃ ) 1.2856g, KBM 503 (Adhesion promoter) 0.2093g, 10wt% BYK 331 (BYK-Chemi) PGMEA solution (Wetting agent solution) 0.2417g, DMF (additional solvent) 26.1921 g of N, N-Dimethyl Formamide) were mixed and stirred at 500 rpm with a stirrer to obtain 70.0000 g of a catalyst composition (solid content 22.19 wt%).

C. Form a fine metal pattern

A catalyst fine metal pattern was formed in the same manner as in the preparation of the fine metal pattern of Example 1, except that the catalyst precursor resin composition prepared in B of Comparative Example 1 and the 5 μm mesh mask were used. The formed metal pattern photo is shown in FIG. 3. As can be seen in the metal pattern of FIG. 3, the metal pattern formed in this comparative example is detached and / or peeled off.

Comparative example  2

A. Preparation of fat-soluble organic polymer resin

2.5 g (18.115 mmol) 1,4-benzenedimethanol, 3.89 g (13.224 mmol) BPDA, 0.196 g (1.322 mmol) THPA (1,2,3,4-Tetrahydropthalic anhydride), and tetrabutylammonium bromide (TBAB) 0.04 g and 12.761 g of PGMEA were added thereto and stirred at 120 ° C. for 9 hours. To remove the remaining BPDA, 0.153 g (1.322 mmol) of HEA (Hydroxyethylacrylate) was added to the reaction mixture, and the reaction mixture was heated to 90 ° C. overnight to obtain a yellow resin solution. The acid value of the organic polymer resin (solid content 34.4 wt%) thus obtained was 183.21 mgKOH / g and the weight average molecular weight was 3,881.

B. Preparation of Catalyst Precursor Resin Compositions

A catalyst precursor resin composition (solid content 22.19 wt%) was prepared in the same manner as the preparation of the catalyst precursor resin composition of Example 1, except that the organic polymer resin prepared in A of Comparative Example 2 was used.

C. Form a fine metal pattern

A catalyst fine metal pattern was formed in the same manner as in the preparation of the fine metal pattern of Example 1, except that the catalyst precursor resin composition prepared in B of Comparative Example 2 and the 5 μm mesh mask were used. The formed metal pattern photo is shown in FIG. 4. As can be seen from the metal pattern of FIG. 4, the metal pattern formed in this comparative example has a problem that the metal pattern is not adhered to the substrate due to insufficient adhesion to the substrate.

1 is a schematic diagram showing a process of forming a fine copper pattern using a photomask process according to the present invention.

FIG. 2 is a photograph showing a metal pattern formed in Example 1. FIG.

3 is a photograph of a metal pattern formed in Comparative Example 1. FIG.

4 is a photograph of a metal pattern formed in Comparative Example 2. FIG.

Claims (28)

(a) a copolymer resin having a carboxylic acid functional group and a cardo functional group, (b) fluorinated silver ion organic complex precursors, (c) a monomer having a polyfunctional ethylenically unsaturated bond, (d) photoinitiators, and (e) Catalyst precursor resin composition for metal pattern formation containing an organic solvent. The copolymer resin according to claim 1, wherein the copolymer resin having a carboxylic acid functional group and a cardo functional group is synthesized by a reaction of a diacid anhydride with at least one selected from the group consisting of dialcohols and diamines having a cardo functional group. A catalyst precursor resin composition. The catalyst precursor resin composition of claim 2, wherein at least one selected from the group consisting of a dialcohol having a cardo functional group and a diamine is selected from the group consisting of Formula 1. [Formula 1]

3. The catalyst precursor resin composition of claim 2, wherein the diacid anhydride is at least one selected from the group consisting of Chemical Formula 2 below. [Formula 2]

The method according to claim 2, wherein at least one selected from the group consisting of a dialcohol and a diamine having the cardo functional group is reacted at 110 to 150 moles based on 100 moles (mol%) of the diacid anhydride. Catalyst precursor resin composition. The catalyst precursor resin composition of claim 1, wherein the copolymer resin has a weight average molecular weight of 2,000-15,000. The catalyst precursor resin composition of claim 1, wherein the copolymer resin has an acid value of 90-300 mg KOH / g. The fluorinated silver ion organic complex according to claim 1, wherein the fluorinated silver ion organic complex is fluorinated silver acetate, fluorinated silver sulfonate, fluorinated β-carbonylketone silver (I) complex and fluorinated β-carbonyl ester A catalyst precursor resin composition, characterized in that at least one selected from the group consisting of a systemic silver (I) complex. The complex of claim 8, wherein the fluorinated silver ion organic complex is a 1,5-cyclooctadiene-hexafluoroacetylacetonatosilver (I) complex, 1,1,1-trifluoro-2,4- Pentanedionenatosilver (I) complexes, 5,5-dimethyl-1,1,1-trifluoro-2,4-hexanediionate silver (I) complexes, 1- (4-methoxyphenyl ) -4,4,4-trifluorobutanedionenetosilver (I) complexes, 5,5,6,6,7,7,8,8,9,10,10,11,12,12, 12-heptadecafluordecane-2,4-dionenetosilver (I) complex 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octane Dionenetosilver (I) complexes, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dionenetosilver (I) complexes, 1,1,1, 5,5,5-hexafluoropentane-2,4-dionenetosilver (I) complexes, 5,5,6,6,7,7,8,8,8-nonafluorooctane-2,4 -Dionenetosilver (I) complexes, 5H, 5H-perfluorononane-4,6-dionenetosilver (I) complexes, 6H, 6H-perfluor-undecane-5,7- Dione Itosilver (I) complex, 8H, 8H-perfluoropentadecane-7,8-dionenetosilver (I) complex, 6H, 6H-perfluorundane-5,7-dionenetosilver (I) Complex, 1-phenyl-2H, 2H-perfluorohexane-1,3-dionenatosilver (I) Complex, 1-phenyl-2H, 2H-perfluorundane-1,3- Dionenetosilver (I) complexes, 5,6,6,6-tetrafluoro-5- (heptafluoropropoxy) hexane-2,4-dionenetosilver (I) complexes, 1,1 , 5,5-tetrafluoropentane-2,4-dione-natosilver (I) complexes, 5,5,6,6,7,7,8,8,9,9,9-undecanefluoro-nonane -2,4-dionenetosilver (I) complex, ethyl 3-chloro-4,4,4-trifluoroacetoacetotosilver (I) complex, ethyl-4,4-difluoroacetoacetate Taytosilver (I) complexes, ethyl-4,4,4-trifluoroacetoacetatetosilver (I) complexes, isopropyl-4,4,4-trifluoroacetoacetatetosilver (I) complexes Water, methyl-4,4,5,5,5-pentafluoro-3-oxopentanoneato Bur (I) complexes, ethyl-4,4,5,5, -pentafluoro-3-oxo-pentanonate silver (I) complexes and 1,1,1,5,5,6,6,6 At least one member selected from the group consisting of octafluor-2,4-hexanedionetosilver (I) complexes. The catalyst precursor resin composition of claim 1, wherein the fluorinated silver ion organic complex precursor is added in an amount of 2 to 40 parts by weight based on 100 parts by weight of the organic solids in the metal pattern forming composition. The method of claim 1, wherein the monomer having a polyfunctional ethylenically unsaturated bond is ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate having a number of ethylene groups of 2 to 14, polyethylene glycol dimethacrylate , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, the number of propylene groups is 2-14 Polyhydric alcohols, such as propylene glycol diacrylate or propylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate The obtained ester to the α, β- unsaturated carboxylic oxidation compounds; Compound obtained by adding acrylic acid or methacrylic acid to a compound containing glycidyl groups such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; β-hydroxyethyl acrylate or β Ester compounds of a polyhydric carboxylic acid with a compound having a hydroxyl group or an ethylenically unsaturated bond such as phthalic acid ester of hydroxyethyl methacrylate; from the group consisting of adducts with multi-polyisocyanates such as compounds having hydroxyl groups or ethylenically unsaturated bonds, such as toluene diisocyanate adducts of β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate Catalyst precursor resin composition, characterized in that at least one selected. The catalyst precursor resin composition according to claim 11, wherein the monomer having a polyfunctional ethylenically unsaturated bond has two or more functional groups having an ethylenically unsaturated bond. The catalyst precursor resin composition of claim 1, wherein the monomer having a polyfunctional ethylenically unsaturated bond is added in an amount of 20 to 150 parts by weight based on 100 parts by weight of the copolymer resin. The method of claim 1, wherein the photoinitiator is at least one member selected from the group consisting of acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, thioxanthones and triazines. A catalyst precursor resin composition. The catalyst precursor resin composition of claim 1, wherein the photoinitiator is used in an amount of 1 to 25 parts by weight based on 100 parts by weight of the copolymer resin. The catalyst of claim 1, wherein the catalyst precursor resin composition further comprises at least one photosensitizer selected from the group consisting of n-butylamine, triethylamine and tri-n-butylphosphine. Precursor resin composition. The catalyst precursor resin composition of claim 16, wherein the photosensitizer is further included in an amount of 10 parts by weight or less based on 100 parts by weight of the copolymer resin and the photoinitiator. The method of claim 1, wherein the organic solvent is alcohol, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and n-methyl-2-pyrrolidone; Aromatic hydrocarbons such as toluene, xylene and 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, dipropylene glycol ethyl ether; Acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol ethyl ether acetate; A catalyst precursor resin composition, characterized in that at least one selected from the group consisting of amides such as N, N-dimethylacetamide, N, N-dimethylformamide, acetonitrile. (a) forming a catalyst precursor pattern on a substrate using the catalyst precursor resin composition of any one of claims 1 to 18; (b) reducing the formed catalyst precursor pattern to form a catalyst pattern; And (c) electroless plating on the catalyst pattern. The resin of claim 19, wherein the substrate is selected from the group consisting of glass, polycarbonate, acrylic resin, PET, tri-acetyl cellulose (TAC), polyvinyl chloride resin, polyamide resin, polyimide resin, and epoxy resin. Metal pattern forming method characterized in that the sheet or film. 20. The method of claim 19, wherein the catalyst pattern forming step is performed by photolithography, offset printing, inkjet printing, imprint or screen printing. 20. The method of claim 19, wherein the reducing step is performed with sodium borane hydride or ascorbic acid reducing agent. 20. The method of claim 19, wherein the reducing step is performed by applying at least one selected from the group consisting of UV exposure and heat. 20. The method of claim 19, wherein the electroless plating is copper plating or silver plating. 25. The method of claim 24, wherein the electroless plating uses a plating solution containing copper sulfate, formalin and EDTA. (a) forming a catalyst precursor pattern on a substrate using the catalyst precursor resin composition of any one of claims 1 to 18; (b) reducing the formed catalyst precursor pattern to form a catalyst pattern; And (c) a metal pattern formed by a metal pattern forming method comprising electroless plating on the catalyst pattern. A part or device comprising the metal pattern of claim 26. An electromagnetic shielding material or a flexible circuit board comprising the metal pattern of claim 26.

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