TW201522071A - Laminate body, conductive pattern, electrical circuit, and method for producing laminate body - Google Patents

Abstract

The present invention provides: a stacked body in which a porous metal layer (B) is formed upon a support body (A), and a metal layer (C) is formed upon the metal layer (B), said stacked body wherein pores in the metal layer (B) are filled with a metal configuring the metal layer (C); and a production method for said stacked body. Also provided are a conductive pattern and an electronic circuit which use the stacked body. In this stacked body, although metal layers of two different kinds are formed upon the support body, excellent adhesive properties are exhibited therebetween.

Description

Laminated body, conductive pattern, circuit, and method of manufacturing laminated body

The present invention relates to a laminate which can be used as a conductive pattern for a printed circuit board, an electromagnetic wave shield, an integrated circuit, an organic transistor, or the like, and a method of manufacturing the same.

In recent years, with the increase in performance, size, and thickness of electronic devices, it is strongly required to increase the density, size, and thickness of circuits and integrated circuits used therefor.

As a conductive pattern which can be used for the above-mentioned circuit or the like, for example, a conductive pattern is known in which a coating agent containing a conductive material is applied onto the surface of a support and fired to form a conductive substance on the surface of the support. In addition, a plating layer is provided on the surface of the conductive material layer by plating the surface of the conductive material layer (see, for example, Patent Documents 1 and 2). However, in the conductive pattern, the adhesion between the conductive material layer and the plating layer is insufficient, and peeling of the plating layer occurs over time, causing a problem of deterioration in conductivity or disconnection.

As described above, as a laminate which can be used as a conductive pattern, it is required that the adhesion of each interface of the support, the conductive material layer, and the plating layer is excellent, in particular, the interface between the conductive material layer and the plating layer is dense. The laminate with excellent properties has not yet been discovered.

[Patent Document 1] Japanese Laid-Open Patent Publication No. 60-246695

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-286158

An object of the present invention is to provide a laminated body in which two types of metal layers are formed on a support, and a method for producing the same, which are excellent in adhesion between the two metal layers. Further, a conductive pattern and a circuit using the laminated body are provided.

In order to solve the above-mentioned problems, the inventors of the present invention have found that if a laminate of two kinds of metal layers is formed on a support, the first metal layer formed on the support is made porous, and the composition is formed. When the metal of the second metal layer on the first metal layer fills the voids existing in the first metal layer, the adhesion between the two metal layers becomes extremely excellent, and the present invention has been completed.

That is, the present invention relates to a laminated body in which a porous metal layer (B) is formed on a support (A) and a metal layer (C) formed on the metal layer (B), and a method for producing the same. The void existing in the metal layer (B) is filled with a metal constituting the metal layer (C). Moreover, the present invention relates to a conductive pattern and a circuit using the laminated body.

Since the adhesion between the two metal layers formed on the support by the laminate system of the present invention is extremely excellent, the conductivity of the metal layer does not decrease with time, and when the metal layer is patterned by a thin line, A disconnection will occur. Therefore, for example, it can be preferably used as a conductive pattern, a circuit, an organic solar cell, an electronic terminal, an organic EL, an organic transistor, or a soft printing. Various components in the field of printed electronic equipment, such as the formation of peripheral wiring such as RFID such as a substrate or a non-contact IC card, the wiring of electromagnetic wave shield of a plasma display, the production of an integrated circuit, and the manufacture of an organic transistor.

Fig. 1 is a cross-sectional photograph of a layered body (1) produced in Example 1 obtained by a scanning electron microscope, and a bright portion indicates a portion in which copper (Cu) atoms are present.

Fig. 2 is a cross-sectional photograph of a layered body (1) produced in Example 1 obtained by a scanning electron microscope, and a bright portion indicates a portion in which silver (Ag) atoms are present.

3 is a cross-sectional photograph of a laminate (R1) produced in Comparative Example 1 by a scanning electron microscope, and a bright portion indicates a portion in which copper (Cu) atoms are present.

4 is a cross-sectional photograph of a laminate (R1) produced in Comparative Example 1 by a scanning electron microscope, and a bright portion indicates a portion in which silver (Ag) atoms are present.

The laminate of the present invention is formed by forming a porous metal layer (B) on the support (A) and forming a metal layer (C) on the metal layer (B), and is present in the metal layer (B). The gap is filled with a metal constituting the metal layer (C).

The support (A) is a substrate which is a laminate of the present invention. Examples of the material of the support (A) include polyimine, polyamide imide, polyamine, polyethylene terephthalate, and polyethylene naphthalate. (polyethylene naphthalate), polycarbonate, acrylonitrile-butadiene-styrene (ABS resin), acrylic tree Grease, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, cellulose nanofiber, enamel, ceramic, glass, glass-ring Oxygen resin, glass polyimide, phenolic paper, and the like.

Moreover, when the laminated body of the present invention is used as a conductive pattern, it is preferable to have an insulating property. Therefore, as the material of the support (A), a phenol resin, a fluororesin, or a polyimine is preferable. Resin, polyethylene terephthalate, polyethylene naphthalate, glass, glass-epoxy resin, glass polyimide, phenolic paper, cellulose nanofiber, alumina, mullite, block talc , magnesium silicate, zirconia, etc.

Further, as the support (A), for example, synthetic fibers such as polyester fibers, polyamide fibers, and aromatic polyamide fibers; and base materials composed of natural fibers such as cotton and hemp may be used. The above fibers may also be processed in advance.

As the support (A), when the laminate of the present invention is used for applications requiring flexibility of flexibility, it is preferred to use a soft and soft support. Specifically, it is preferred to use a film or a sheet-shaped support.

Examples of the film or sheet-like support include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.

When the shape of the support (A) is a film or a sheet, the thickness of the film-like or sheet-shaped support is usually preferably about 1 to 5,000 μm, more preferably about 1 to 300 μm. In the case where the laminate of the present invention is used for a bender such as a flexible printed circuit board, it is preferable to use a film having a thickness of about 1 to 200 μm as the support.

In order to further improve the adhesion to the metal layer (B), the surface of the support (A) may be subjected to a plasma discharge treatment such as a corona discharge treatment or ultraviolet. The surface treatment is carried out by a dry treatment method such as a line treatment method or a wet treatment method using water, an acidic or alkaline chemical solution, or an organic solvent.

The metal layer (B) is a porous one formed on the support (A), and has a void in the layer. The metal constituting the metal layer (B) may, for example, be a transition metal or a compound thereof, and among them, an ionic transition metal is preferred. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, cobalt, and the like. Among the plasma transition metals, copper, silver, and gold are preferred because they have a conductive pattern having low electrical resistance and corrosion resistance.

Further, examples of the metal constituting the metal layer (C) include copper, nickel, chromium, cobalt, tin, and the like. Among these, copper is preferable because it can obtain a conductive pattern having low electrical resistance and corrosion resistance.

In the laminate of the present invention, the voids present in the metal layer (B) are filled with a metal constituting the metal layer (C), and the metal constituting the metal layer (C) is filled in the support (A) and the above The voids in the metal layer (B) in the vicinity of the interface of the metal layer (B) are preferably improved because the adhesion between the metal layer (B) and the metal layer (C) can be further improved.

The method for producing the layered product of the present invention includes, for example, a method in which a fluid containing a metal powder of a nanometer size and a dispersing agent is applied onto a support (A) and fired to form a metal layer (B'). Thereafter, the organic compound containing the dispersing agent in the metal layer (B') is removed to form a void, and the porous metal layer (B) is formed, and then the metal layer (C) is formed by electrolysis or electroless plating.

The shape of the metal powder for forming the nanometer size of the metal layer (B) may be any shape as long as the metal layer is porous, and is preferably particulate or fibrous. Again, on When the size of the metal powder is a nanometer size, specifically, when the shape of the metal powder is particulate, since a fine conductive pattern can be formed, the resistance value after firing can be further reduced, so the average particle size The diameter is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm. Further, the above "average particle diameter" is a volume average value measured by a dynamic light scattering method by diluting the above-mentioned conductive material with a dispersion good solvent. For the measurement, "Nanotrac UPA-150" manufactured by Microtrac Co., Ltd. can be used.

On the other hand, when the shape of the metal powder is fibrous, since the fine conductive pattern can be formed, the resistance value after firing can be further reduced, so the diameter of the fiber is preferably in the range of 5 to 100 nm, more preferably It is in the range of 5 to 50 nm. Further, the length of the fiber is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.1 to 30 μm.

When the metal layer (B) is formed on the support (A), a method of applying a fluid having the above-described nano-sized metal powder in a solvent to the support (A) is preferred.

The content ratio of the above-mentioned nano-sized metal powder in the above-mentioned fluid is preferably in the range of 5 to 90% by mass, more preferably in the range of 10 to 60% by mass.

As a component to be blended in the above-mentioned fluid, a dispersant or a solvent for dispersing a metal powder of a nanometer size in a solvent, and optionally a surfactant, a leveling agent, a viscosity modifier, and a film formation are included. Organic compounds such as auxiliaries, defoamers, and preservatives.

In order to disperse the above-mentioned nano-sized metal powder in a solvent, a low molecular weight or high molecular weight dispersant is used. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, and poly Vinyl pyrrolidone; fatty acids such as myristic acid, caprylic acid, stearic acid; cholic acid, licorice A polycyclic hydrocarbon compound having a carboxyl group such as an acid or a rosin acid. Among these, by increasing the size of the voids in the metal layer (B), the adhesion between the metal layer (B) and the metal layer (C) described below can be improved, so that a polymer dispersant is preferred. The polymer dispersant is preferably a polyalkyleneimine such as polyethyleneimine or polypropyleneimine, or a compound obtained by adding the above-mentioned polyalkyleneimine to a polyoxyalkylene group.

As described above, since the polymer dispersant is used in the dispersant, the void size formed by removing the dispersant in the metal layer (B) can be increased as compared with the low molecular dispersant, and the self-nano grade can be formed. The gap to the size of the micron. It is easy to fill the voids with the metal constituting the metal layer (C) described below, and the filled metal serves as an anchor, and the adhesion between the metal layer (B) and the metal layer (C) described below can be greatly improved.

The amount of the above-mentioned dispersant used for dispersing the above-mentioned nano-sized metal powder is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the metal powder of the above nanometer size. .

Further, since the dispersant in the metal layer (B) can be removed, voids are more easily formed, and the adhesion between the metal layer (B) and the metal layer (C) described below is further improved, so that the nanometer size is The metal powder is 100 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

As the solvent used for the above fluid, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion-exchanged water, pure water, and ultrapure water. Further, examples of the organic solvent include an alcohol compound, an ether compound, an ester compound, and a ketone compound.

Examples of the above alcohol include methanol, ethanol, 1-propanol, and 2-propanol. 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, heptanol, hexanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, Dodecanol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, stearyl alcohol, allyl alcohol, cyclohexanol, rosinol, rosinol, dihydroterpineol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, two Propylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, and the like.

Further, in addition to the metal powder and the solvent, ethylene glycol, diethylene glycol, 1,3-butylene glycol, isoprene glycol or the like may be used as the above-mentioned fluid.

As the above surfactant, a usual surfactant can be used, and examples thereof include di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, and alkyldiphenyloxide disulfonate. , alkyl naphthalene sulfonate, hexametaphosphate, and the like.

As the leveling agent, a usual leveling agent can be used, and examples thereof include a polyoxymethylene compound, an acetylene glycol compound, and a fluorine compound.

As the viscosity adjusting agent, a usual tackifier can be used. For example, an acrylic polymer or a synthetic rubber latex which can be viscosified by being adjusted to be alkaline, and an amine group which can be viscosified by molecular aggregation can be used. An acid ester resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, guanamine wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol, and the like.

As the film-forming auxiliary agent, a usual film-forming auxiliary agent can be used, and examples thereof include an anionic surfactant (dioctylsulfosuccinate sodium salt) and a hydrophobic nonionic surfactant (sorbent pear). Alcohol anhydride monooleate, etc., polyether modified oxirane, polyoxyxene oil, and the like.

As the antifoaming agent, a usual antifoaming agent can be used, and examples thereof include a polyfluorene-based antifoaming agent, a nonionic surfactant, a polyether, a higher alcohol, and a polymer-based surfactant.

As the above-mentioned preservative, a usual preservative can be used, and for example, an isothiazoline-based preservative, three An antiseptic, an imidazole preservative, a pyridine preservative, an azole-based preservative, an iodine-based preservative, a pyrithione-based preservative, and the like.

The viscosity of the above fluid (measured by using a B-type viscometer at 25 ° C) is preferably in the range of 0.1 to 500,000 mPa ‧ , more preferably 0.5 to 10,000 mPa ‧ s. Further, when the fluid is applied (printed) by a method such as the following ink jet printing method or letterpress reverse printing, the viscosity is preferably in the range of 5 to 20 mPa ‧ s.

Examples of the method of applying the fluid to the support (A) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, and a spin coating method. , spray coating method, bar coating method, die coating method, slit coating method, roll coating method, dip coating method, and the like.

In the case of forming the metal layer (B) in which a thin line having a width of about 0.01 to 100 μm required to achieve a high density of a circuit or the like is formed, it is preferable to use it. Inkjet printing method, reverse printing method.

As the above inkjet printing method, a person generally referred to as an inkjet printer can be used. Specific examples thereof include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatix Materials Printer DMP-3000, Dimatix Materials Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like.

Further, as a reverse printing method, a letterpress reverse printing method and a gravure reverse printing method are known. The method may, for example, be a method of applying the fluid to the surface of each of the blankets, contacting the plate of the non-line portion, and selectively transferring the fluid corresponding to the non-line portion to the plate. The surface is formed on the surface of the blanket or the like, and then the pattern is transferred onto the support layer (A) (surface).

The metal layer (B) is formed on the support (A), and may be on the surface of the support (A) in order to further improve the adhesion between the surface of the support (A) and the metal layer (B). A primer is applied and dried to form a primer layer, and then the metal layer (B) is formed on the primer layer.

Examples of the primer include a urethane resin, a vinyl resin, a urethane-vinyl composite resin, an epoxy resin, a quinone imide resin, a guanamine resin, a melamine resin, and a phenol resin. , various resins and solvents such as polyvinyl alcohol and polyvinylpyrrolidone.

Among the resins used as the primer described above, it is preferred to use a urethane resin, a vinyl resin, a urethane-vinyl composite resin, and more preferably an ureidocarboxylic acid having a polyether structure. One or more of a group consisting of an ester resin, a urethane resin having a polycarbonate structure, a urethane resin having a polyester structure, an acrylic resin, and a urethane-acrylic composite resin The resin, the urethane-acrylic composite resin is more preferable because a laminate which is used for a conductive pattern having excellent adhesion, conductivity, and fine linearity can be obtained.

The content ratio of the above-mentioned resin in the above primer is preferably in the range of 10 to 70% by mass, and more preferably in the range of 10 to 50% by mass, in consideration of ease of application.

Moreover, as a solvent used for the said primer, an organic solvent or an aqueous medium is mentioned.

Examples of the organic solvent include toluene, ethyl acetate, and methyl ethyl Examples of the aqueous medium include a water, a water-miscible organic solvent, and a mixture thereof.

Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve; acetone and methyl ethyl ketone; Ketones; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ethers of polyalkylene glycol; and decylamine such as N-methyl-2-pyrrolidone.

The content ratio of the solvent in the primer is preferably in the range of 25 to 85% by mass, and more preferably in the range of 45 to 85% by mass, in consideration of ease of application.

In the above primer, additives such as a crosslinking agent, a pH adjusting agent, a film forming aid, a leveling agent, a tackifier, a water repellent, and an antifoaming agent may be added as needed.

The primer layer may be formed by applying a primer to a part or all of the surface of the support (A) to remove a solvent such as an aqueous medium or an organic solvent contained in the primer.

Examples of the method of applying the primer to the surface of the support (A) include a gravure method, a coating method, a screen pattern, a roll method, a rotation method, and a spray method.

In order to further improve the adhesion to the metal layer (B), the surface of the primer layer may be, for example, a dry treatment such as a plasma discharge treatment method such as a corona discharge treatment method or an ultraviolet treatment method, or the like. The surface treatment is carried out by a wet treatment method of water, an acidic or alkaline chemical solution, an organic solvent or the like.

The method of removing the solvent contained in the coating layer after applying the primer to the surface of the support (A) is, for example, a method in which drying is carried out by using a dryer to volatilize the solvent. As the drying temperature, it is preferably set to volatilize the above solvent, and it is not correct The temperature at which the support (A) causes a bad influence.

The thickness of the primer layer formed by using the above primer differs depending on the use of the laminate of the present invention, and since the adhesion between the support (A) and the metal layer (B) can be further improved, it is preferably The range of 10 nm to 30 μm is more preferably in the range of 10 nm to 1 μm, and even more preferably in the range of 10 nm to 500 nm.

Further, when the primer layer is provided on the support (A), since the adhesion between the support (A) and the primer layer can be improved, the surface of the support (A) can be used. Surface treatment for forming fine concavities and convexities, cleaning stains adhering to the surface, and introducing a functional group such as a hydroxyl group, a carbonyl group or a carboxyl group is carried out. Specifically, a dry treatment such as a plasma discharge treatment such as a corona discharge treatment or an ultraviolet treatment, or a wet treatment using an aqueous solution such as water or an acid or an organic solvent, or the like may be performed.

In order to form the metal layer (B), the firing step performed after applying the fluid containing the metal powder is performed by bonding the metal powder contained in the fluid body to each other to form a conductive layer. The metal layer (B) is carried out. The firing is preferably carried out at a temperature ranging from 80 to 300 ° C for about 2 to 200 minutes. The firing may be carried out in the air, and some or all of the firing step may be carried out under a reducing atmosphere in order to prevent oxidation of the metal powder. By the baking step, the particulate or fibrous metal powder for forming the metal layer (B) is bonded to each other and joined, whereby the metal layer (B) is porous.

Further, the firing step can be carried out, for example, using an oven, a hot air drying oven, an infrared drying oven, laser irradiation, microwave, light irradiation (flash irradiation device), or the like.

The thickness of the metal layer (B') obtained by the above-described firing step is preferably in the range of 10 nm to 10 μm in consideration of adhesion to the metal layer (C) described below, and more preferably The range of 10 nm to 3 μm.

After the firing step, the organic compound containing the dispersing agent in the metal layer (B') is removed to form a void, whereby the porous metal layer (B) can be formed. As a method of removing the organic compound, the metal layer (B') is subjected to a plasma discharge treatment method, an electromagnetic wave irradiation treatment method, a laser irradiation treatment method, and the organic compound containing the dispersant is redispersed with water or an organic solvent. A method of treatment such as dissolution treatment. These treatment methods may be used singly or in combination of two or more kinds, and it is preferable to use two or more types in combination to remove the organic compound more efficiently. In addition, the organic compound described herein is a component blended in the above-mentioned fluid, and means a dispersant, a solvent, a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, Organic compounds such as preservatives.

Examples of the plasma discharge treatment method include a normal piezoelectric slurry discharge treatment method such as a corona discharge treatment method, and a vacuum plasma discharge treatment such as a glow discharge treatment method and an arc discharge treatment method performed under vacuum or reduced pressure. Law and so on.

The above-described normal piezoelectric slurry discharge treatment method is a method of performing plasma discharge treatment in an environment having an oxygen concentration of about 0.1 to 25% by volume, in order to improve adhesion between the metal layer (B) and the metal layer (C). And it is easy to fill the metal constituting the metal layer (C) with the voids of the porous metal layer (B), preferably having an oxygen concentration of 10 to 22% by volume, more preferably about 21% by volume (air) in environment).

Further, when the normal piezoelectric slurry discharge treatment method is carried out in an atmosphere containing an inert gas at the oxygen concentration, the metal layer (B) can be further increased without imparting excessive unevenness to the surface of the metal layer (B). It is preferable because it has adhesion to the metal layer (C). Further, examples of the inert gas include argon gas, nitrogen gas, and the like.

The apparatus which can be used for the treatment by the above-described normal piezoelectric slurry discharge treatment method is, for example, a normal piezoelectric slurry processing apparatus "AP-T01" manufactured by Sekisui Chemical Co., Ltd., and the like.

When the treatment is carried out by the above-described normal piezoelectric slurry discharge treatment method, the flow rate of the gas such as air is preferably in the range of 5 to 50 liters/min. Further, as the output, it is preferably in the range of 50 to 500 W. Further, the processing time is preferably in the range of 1 to 500 seconds.

Among the above-described normal piezoelectric slurry discharge treatment methods, a corona discharge treatment method is preferably used. As a device which can be used for the corona discharge treatment method, for example, a corona surface modification evaluation device "TEC-4AX" manufactured by Kasuga Electric Co., Ltd., or the like can be cited.

When it is processed by the corona discharge treatment method, it is preferably in the range of 5 to 300 W as an output. Further, the processing time is preferably in the range of 0.5 to 600 seconds.

In the above plasma discharge treatment method, since the organic compound present in the metal layer (B') can be removed deep, it is possible to exist even in the vicinity of the interface between the support (A) and the metal layer (B). The organic compound present in the metal layer (B) is preferably removed. When the following metal layer (C) is formed by using the above-described plasma discharge treatment method, it is easy to fill the metal constituting the metal layer (C) with the voids of the porous metal layer (B), and it is easier to form the metal layer ( The metal of C) is filled into the voids in the metal layer (B) present in the vicinity of the interface between the support (A) and the metal layer (B). Thereby, the metal constituting the metal layer (C) enters the deeper portion of the metal layer (B) to exert a larger anchoring effect, so that the metal layer (B) and the metal layer (C) described below can be greatly improved. Adhesion.

In the electromagnetic wave irradiation treatment method described above, by irradiating the metal layer (B') with an electromagnetic wave, the metal layer (B') can be heated at a high temperature to decompose and remove the organic compound. The The electromagnetic wave irradiation treatment can also selectively remove the dispersant by electromagnetic wave absorption resonance. The wavelength of the electromagnetic wave resonating with the organic compound present in the metal layer (B') is set in advance, and the metal layer (B) is irradiated with an electromagnetic wave of a predetermined wavelength. Thereby, the absorption of the above organic compound becomes large (resonance), so that only the dispersant can be removed by adjusting the intensity of the electromagnetic wave.

In the laser irradiation treatment method described above, the organic compound in the metal layer (B') can be decomposed and removed by irradiating the metal layer (B') with a laser. In the laser irradiation treatment method, a laser that can perform laser scribing processing can be used. Examples of the laser that can perform laser scribing processing include a YAG laser, a CO ₂ laser, a pseudo-molecular laser, and the like, and a YAG laser. In addition to the fundamental wavelength of 1.06 μm, light of 0.53 μm of the second harmonic obtained by using a non-linear optical element may be used as needed. Regarding YAG lasers, pulsed lasers are preferred because of the higher peak power and higher frequencies.

Specifically, the metal layer (B') is irradiated with a laser beam, and while the metal layer (B') is transferred, the laser beam output from the laser light source is condensed by the lens to the metal layer (B). The surface of ') is irradiated. At this time, the laser beam is moved by the polygon mirror, and the surface of the metal layer (B') in the conveyance is scanned by the laser beam. Thereby, the metal layer (B') can be heated at a high temperature. Regarding the laser irradiation treatment, it is preferable that the output of the laser light is 0.1 to 100 kW, the frequency of the pulse transmission (oscillation frequency) is several kHz to several tens of kHz, and the continuous time (pulse width) of one pulse is 90 to 100 nsec.

The dissolution treatment method is a method in which the organic compound present in the metal layer (B') is redispersed and dissolved in water or an organic solvent. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, and isopropyl alcohol; aprotic polar solvents such as dimethyl hydrazine, dimethylformamide, and N-methylpyrrolidone; tetrahydrofuran and Base ethyl ketone, B Ethyl acetate, Equamide (organic solvent manufactured by Idemitsu Kosan Co., Ltd.).

Further, in order to redisperse and dissolve the above organic compound, it is preferred to use an acid or a base, and it is more preferred to use a base. Examples of the acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, and adipic acid. Among these, a strong acid such as sulfuric acid, nitric acid or hydrochloric acid is preferably used. Further, in the case where the following metal layer (C) is formed by the electrolytic copper plating step using copper sulfate, sulfuric acid is preferably used in order not to carry impurities in the subsequent step.

Examples of the base include organic amines such as sodium hydroxide or potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia, triethylamine, pyridine, and phegfraline; and alkanolamines such as monoethanolamine. Among them, a strong base such as sodium hydroxide or potassium hydroxide is preferably used.

Further, a surfactant may be used in order to redisperse and dissolve the above organic compound. As the above surfactant, a usual surfactant can be used, and examples thereof include di-2-ethylhexylsulfosuccinate, alkyl sulfate, alkylbenzenesulfonate, and alkyl diphenyl ether disulfonate. Acid salt, etc. These surfactants are more preferably formed by being dissolved in water to exhibit alkalinity, and thus it is easy to remove the above organic compound.

Next, as described above, a porous metal layer (B) having voids by removing the organic compound in the metal layer (B') is formed on the support (A), and then the metal layer (B) is formed. The metal layer (C) is formed thereon, whereby the laminate of the present invention can be obtained.

The metal layer (C) constituting the laminate of the present invention is, for example, a layer provided for the purpose of forming the laminate in the case of a conductive pattern or the like, and forming a laminate which can be prevented from being broken for a long period of time, and is maintained in a good manner. Wiring pattern with high reliability of electrification.

The metal layer (C) is a layer formed on the metal layer (B) as The method of forming the film is preferably a method of forming by a plating treatment. Examples of the plating treatment include a wet plating method such as a plating method and an electroless plating method, and a dry plating method such as a sputtering method or a vacuum vapor deposition method. Further, two or more kinds of plating methods may be combined to form the metal layer (C).

In the plating treatment described above, it is easy to fill the metal constituting the metal layer (C) by the voids in the porous metal layer (B), and the adhesion between the metal layer (B) and the metal layer (C) is further improved. Further, a conductive pattern having excellent conductivity can be obtained. Therefore, a wet plating method such as an electroplating method or an electroless plating method is preferred, and a plating method is more preferred.

The electroless plating method is, for example, a method in which an electroless plating solution is brought into contact with a metal constituting the metal layer (B) to deposit a metal such as copper contained in the electroless plating solution to form an electroless plating layer made of a metal film ( Film).

Examples of the electroless plating solution include metals such as copper, nickel, chromium, cobalt, and tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent.

Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, and phenol.

Further, as the electroless plating solution, a dicarboxylic acid such as acetic acid or formic acid, a dicarboxylic acid such as malonic acid, succinic acid, adipic acid, maleic acid or fumaric acid may be used as needed. Compound, hydroxycarboxylic acid compound such as malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, amino acid such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, glutamic acid An organic acid such as an amine-based polycarboxylic acid compound such as a compound such as a nitrogen triacetic acid, an ethylenediamine diacetic acid, an ethylenediaminetetraacetic acid or a diethylenetriaminepentaacetic acid; or a soluble salt of the organic acid (sodium salt, Potassium salts, ammonium salts, etc.;; amine diamines such as ethylenediamine, di-ethyltriamine, and tri-extension ethyltetramine.

The electroless plating solution is preferably used in the range of 20 to 98 °C.

The plating method is a method in which, for example, a plating solution is used to contact a metal constituting the metal layer (B) or a surface of the electroless plating layer (film) formed by the non-electrolytic treatment, thereby energizing the plating solution. A metal such as copper is deposited on the surface of the electroless plating layer (film) constituting the metal layer (B) provided as a cathode or the electroless plating layer (film) formed by the above electroless treatment to form a plating layer (metal film).

Examples of the plating solution include a sulfide containing a metal such as copper, nickel, chromium, cobalt, or tin, sulfuric acid, and an aqueous medium. Specific examples include those containing copper sulfate, sulfuric acid, and an aqueous medium.

The above plating solution is preferably used in the range of 20 to 98 °C.

In the above plating treatment method, since a highly toxic substance is not used and workability is good, it is preferable to form a metal layer (C) made of copper by an electroplating method.

Further, as the dry plating treatment step, a sputtering method, a vacuum deposition method, or the like can be used. The sputtering method is a method of introducing an inert gas (mainly argon gas) into a vacuum, applying a voltage to a material (target) of the metal layer (C), generating a glow discharge, and secondly, causing the inert gas atom Ionization, the surface of the material (target) of the metal layer (C) is strongly impinged on the gas ions at a high speed, and the atoms and molecules constituting the material (target) constituting the metal layer (C) are ejected, and the gas potential is strong. The ground is adhered to the surface of the above metal layer (B), thereby forming a metal layer (C).

Examples of the material (target) of the metal layer (C) formed by the sputtering method include chromium, copper, titanium, silver, platinum, gold, nickel-chromium alloy, stainless steel, and copper-zinc alloy. Indium tin oxide (ITO), cerium oxide, titanium dioxide, cerium oxide, zinc oxide, and the like.

When the plating treatment is performed by the above sputtering method, for example, a magnetron sputtering apparatus or the like can be used.

The thickness of the metal layer (C) is preferably in the range of 1 to 50 μm. The thickness of the metal layer (C) can be adjusted by controlling the processing time of the plating treatment step when the metal layer (C) is formed, the current density, the amount of the additive for plating, and the like.

The laminate of the present invention obtained by the above method can be used as a conductive pattern. In the case where the laminate of the present invention is used for a conductive pattern, in order to form the metal layer (B) at a position corresponding to a desired pattern shape to be formed, a fluid containing the metal powder is applied and By firing, a conductive pattern having a desired pattern can be produced.

Further, the conductive pattern may be plated by, for example, a photolithography-etching method such as a subtractive process or a semi-additive process, or a printed pattern on the metal layer (B). The method of manufacture.

The above-mentioned subtractive method is a method of forming an etching resist layer corresponding to a shape of a desired pattern shape on the above-mentioned metal layer (C) constituting the laminated body of the present invention, which is previously manufactured, and developing treatment thereafter The metal layer (C) and the metal layer (B) in which the resist is removed are dissolved and removed by a chemical solution to form a desired pattern. As the above-mentioned chemical liquid, a chemical liquid containing copper chloride, iron chloride or the like can be used.

The semi-additive method is a method in which the metal layer (B') is formed on the support (A), and if necessary, the dispersant is contained in the metal layer (B') by plasma discharge treatment or the like. After the organic compound, a plating resist layer corresponding to the shape of the desired pattern is formed on the surface of the obtained metal layer (B), and secondly, after the metal layer (C) is formed by electroplating or electroless plating, The plating resist layer and the metal layer (B) in contact therewith are dissolved in the medicine The liquid is removed, etc., thereby forming a desired pattern.

Moreover, the method of performing plating on the printing pattern of the metal layer (B) is a method of printing the pattern of the metal layer (B) on the support (A) by an inkjet method, a reverse printing method, or the like, as needed. After removing the organic compound containing the dispersing agent in the metal layer (B') by plasma discharge treatment or the like, the metal is formed on the surface of the obtained metal layer (B) by electroplating or electroless plating. Layer (C), thereby forming the desired pattern.

With regard to the conductive pattern obtained by the above method, the adhesion between the respective layers, in particular, the adhesion between the metal layer (B) and the metal layer (C) is extremely high, so that interlayer peeling can be suppressed. It can be used for the formation of a substrate for circuit formation using a circuit such as a silver ink or an integrated circuit, and can be used for forming an organic solar cell, an electronic terminal, an organic EL, an organic transistor, or a soft one. The formation of peripheral wiring of a printed circuit board, an RFID, etc., and the wiring of electromagnetic wave shield of a plasma display. In particular, it can be preferably used for applications requiring high durability, for example, for printed wiring boards (PWB), flexible printed boards (FPC), tape-and-tape automatic bonding (TAB), film over-molding (COF), and the like.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples.

[Preparation of primer]

In a reaction flask equipped with a reflux condenser, a thermometer, and a stirrer, 600 parts by mass of formalin added to 37% by mass of formaldehyde and 7% by mass of methanol (formaldehyde content: 222 parts by mass (7.4 mol), methanol content: 42 mass A portion (1.31 mol) of a solution obtained by adding 200 parts by mass of water and 350 parts by mass of methanol (10.92 mol) to make it uniform. Next, after adding a 25% by mass aqueous sodium hydroxide solution to adjust the pH to 10, 310 parts by mass of melamine (2.46 mol) was added to raise the liquid temperature. The methylolation reaction was carried out to 85 ° C (reaction time: 1 hour).

Thereafter, the formic acid was adjusted to pH 7, and then cooled to 60 ° C to carry out an etherification reaction. A 25 mass% sodium hydroxide aqueous solution was added at a cloud temperature of 40 ° C to adjust the pH to 9, and the etherification reaction was stopped (reaction time: 1 hour). The methanol remaining under reduced pressure at a temperature of 50 ° C was removed (demethylation time: 4 hours) to obtain a melamine resin-containing primer having a nonvolatile content of 80% by mass.

Further, regarding the measurement method of the white turbidity temperature, 1 g of a resin was taken, and the resin was mixed with 100 ml of water adjusted to a predetermined temperature. At this time, the temperature of the highest water when the resin was insoluble in water and white turbidity was set to a white turbid temperature.

[Preparation of fluid (1)]

A compound obtained by adding polyethyleneimine and polyoxyethylene as a dispersing agent, and dispersing silver particles having an average particle diameter of 30 nm in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water, thereby preparing A flow body (1) containing a metal powder of nanometer size and a dispersing agent.

[Preparation of fluid (2)]

The flow body (1) obtained as described above was prepared by using ion-exchanged water and a surfactant, and adjusting the viscosity to 10 mPa ‧ to prepare a fluid (2) as a conductive ink for inkjet printing.

[Example 1]

The primer prepared as described above was applied to a polyimide film (Kapton 200H, manufactured by Toray DuPont Co., Ltd., thickness: 50 μm) by using a spin coater to a thickness of 0.1 μm after drying. The surface of the support that constitutes it. Next, it was dried at 120 ° C for 5 minutes using a hot air dryer to form a primer layer on the surface of the polyimide film.

Second, use an inkjet printer (Konica Minolta I J Co., Ltd. The ink jet tester EB100, the print head KM512L for evaluation, the discharge amount of 42 pL), and the flow body (2) obtained above was applied to the surface of the primer layer, and the entire surface was coated at an area of 10 cm in length and 5 cm in width. cloth. Next, by firing at 250 ° C for 30 minutes, a silver layer (thickness of about 1 μm) corresponding to the above metal layer (B') was formed.

Next, a treatment for removing the organic compound in the silver layer corresponding to the above metal layer (B') is performed. First, as a plasma discharge treatment method, a corona surface modification evaluation device ("TEC-4AX" manufactured by Kasuga Electric Co., Ltd.) is used to perform corona discharge on the surface of the silver layer corresponding to the metal layer (B'). Treatment (gas: air (oxygen concentration: about 21% by mass), gap: 1.5 mm, output: 100 W, treatment time: 2 seconds). Next, as a dissolution treatment method, the organic compound was removed by treatment with an alkaline surfactant at a liquid temperature of 40 ° C for 5 minutes to obtain a silver layer corresponding to the metal layer (B) having a porous void. As the alkaline surfactant, the ICP cleaning solution SC (manufactured by Okuno Pharmaceutical Co., Ltd.) was diluted to 150 ml/L (pH = 9.3).

Next, the silver layer corresponding to the metal layer (B) obtained above was set as a cathode, phosphorus-containing copper was set as an anode, and a plating solution containing copper sulfate was used for plating for 15 minutes at a current density of 2 A/dm ² . This is a copper plating layer having a surface layer thickness of 8 μm in the above silver layer. As the plating solution, 70 g/L of copper sulfate, 200 g/L of sulfuric acid, 50 mg/L of chloride ion, and 5 ml/L of "additive (Top Lucina SF-M) manufactured by Okuno Pharmaceutical Co., Ltd.) were used.

By the above method, a layered body (1) in which each layer is laminated in the order of a support (A), a primer layer, a metal layer (B), and a metal layer (C) is obtained. With respect to the obtained laminate (1), a cross section was confirmed using a scanning electron microscope ("JSM-7800F" manufactured by JEOL Ltd.). A photograph of the cross section of the laminate (1) is shown in Fig. 1 (copper (Cu) map) and Fig. 2 (silver) (Ag) mapping). According to the comparison between FIG. 1 and FIG. 2, in the silver layer corresponding to the metal layer (B), copper (Cu) atoms constituting the metal layer (C) are also present, and the copper atoms reach the silver corresponding to the metal layer (B). It is confirmed that the copper as the metal constituting the metal layer (C) is filled in the void of the metal layer (B) until reaching the metal layer (B) and the support (A). Near the interface.

[Embodiment 2]

The electromagnetic wave irradiation treatment (wavelength: 100 μm) was carried out in the same manner as in Example 1 except that the treatment by the corona surface modification evaluation device ("TEC-4AX" manufactured by Kasuga Electric Co., Ltd.) was performed. The laminate (2) in which the support (A), the primer layer, the metal layer (B), and the metal layer (C) are laminated in this order. The laminate (2) obtained was observed by a scanning electron microscope in the same manner as in Example 1. As a result, it was confirmed that copper as a metal constituting the metal layer (C) was filled in the void of the metal layer (B) until reaching the metal. Near the interface between layer (B) and support (A).

[Example 3]

Laser irradiation treatment (output 6 kW) is used instead of the treatment by the corona surface modification evaluation device ("TEC-4AX" manufactured by Kasuga Electric Co., Ltd.) and the treatment by the ICP cleaning liquid. In the same manner as in Example 1, the support (A), the primer layer, the metal layer (B), and the laminate (3) corresponding to the laminated layer of the metal layer (C) were obtained. The laminate (3) obtained was observed by a scanning electron microscope in the same manner as in Example 1. As a result, it was confirmed that copper as a metal constituting the metal layer (C) was filled in the void of the metal layer (B) until reaching the metal. Near the interface between layer (B) and support (A).

[Example 4]

The same treatment as in Example 1 was carried out except that the treatment was carried out in a sulfuric acid (60 ml/L) for 5 minutes instead of the treatment by the corona surface modification evaluation device ("TEC-4AX" manufactured by Kasuga Electric Co., Ltd.). The layered body (4) in which the layers are laminated in the order of the support (A), the primer layer, the metal layer (B), and the metal layer (C) is obtained. The laminate (4) obtained was observed by a scanning electron microscope in the same manner as in Example 1. As a result, it was confirmed that copper as a metal constituting the metal layer (C) was filled in the void of the metal layer (B) until reaching the metal. Near the interface between layer (B) and support (A).

[Comparative Example 1]

The primer prepared above was applied to a polyimide film (Kapton 200H, manufactured by Toray DuPont Co., Ltd., thickness: 50 μm) by a spin coater so as to have a thickness of 0.1 μm after drying. The surface of the support. Next, a primer layer was formed on the surface of the polyimide film by drying at 120 ° C for 5 minutes using a hot air dryer.

Next, silver was provided as a target on the surface of the primer layer, and a silver layer having a thickness of about 1 μm was formed by magnetron sputtering using a direct current voltage between the substrate and the target while introducing argon under vacuum.

Next, the silver layer obtained above was set as a cathode, phosphorus-containing copper was set as an anode, and plating liquid containing copper sulfate was used for electroplating at a current density of 2 A/dm ² for 15 minutes, thereby forming a surface layer thickness of the above silver layer. 8μm copper plating layer. As the plating solution, 70 g/L of copper sulfate, 200 g/L of sulfuric acid, 50 mg/L of chloride ion, and 5 ml/L of "additive (Top Lucina SF-M) manufactured by Okuno Pharmaceutical Co., Ltd.) were used.

By the above method, a layered body (R1) in which each layer is laminated in the order of a support (A), a primer layer, a silver layer, and a copper layer is obtained. A photograph of the cross section of the laminate (R1) is shown in the figure. 3 (copper (Cu) mapping) and Figure 4 (silver (Ag) mapping). According to the comparison between FIG. 3 and FIG. 4, in the silver layer corresponding to the metal layer (B), copper (Cu) atoms constituting the metal layer (C) are not present, so that it is confirmed that the metal constituting the metal layer (C) The copper does not enter the metal layer (B) at all. Further, a cross-sectional photograph of the laminated body (R1) is shown in Figs. 3 and 4.

<Evaluation of adhesion by peel strength measurement>

The peel strength was measured by the method according to IPC-TM-650, NUMBER2.4.9. The lead width for measurement was 1 mm, and the angle of peeling was set to 90°. Further, the peel strength tends to be higher as the thickness of the plating layer is higher, and the peel strength in the present invention is measured based on the measured value of the plating layer of 8 μm which is now common.

<Evaluation by visual adhesion>

The peeled surface after the measurement of the peel strength was visually observed, and the position of the peeled interface was confirmed. The position of the peeled interface was set to 1 to 3 below, and when the position of the peeled interface was 2 or 3, the adhesion between the metal layer (B) and the metal layer (C) was judged to be good.

1: interface between metal layer (B) and metal layer (C)

2: interface between the primer layer and the metal layer (B)

3: interface between the primer layer and the polyimide film (support)

The results of the evaluation results obtained above are summarized in Table 1.

The laminates (1) to (4) obtained in Examples 1 to 4 which are the laminates of the present invention have high peel strength because they are not peeled off from the interface between the metal layer (B) and the metal layer (C). It was confirmed that the adhesion between the metal layer (B) and the metal layer (C) was extremely high.

On the other hand, the laminate (R1) obtained in Comparative Example 1 is an example in which the silver layer corresponding to the metal layer (B) is not porous. Since the laminate (R1) is peeled off from the interface between the silver layer (corresponding to the metal layer (B)) and the copper layer (corresponding to the metal layer (C)), it can be confirmed that the adhesion between the two metal layers is not practical. .

Claims (9)

A laminated body obtained by forming a porous metal layer (B) on a support (A) and forming a metal layer (C) on the metal layer (B), characterized in that it exists in the metal layer The void in (B) is filled with a metal constituting the metal layer (C). The laminate according to claim 1, wherein the metal constituting the metal layer (C) is filled in the metal layer (B) existing in the vicinity of the interface between the support (A) and the metal layer (B). The gap. The laminate according to the first aspect of the invention, wherein the metal constituting the metal layer (B) is silver, and the metal constituting the metal layer (C) is copper. The laminate according to claim 1, wherein the support (A) and the metal layer (B) are laminated via a primer layer. A conductive pattern consisting of the laminate of any one of claims 1 to 4. A circuit having a conductive pattern of claim 5 of the patent application. A method for producing a laminate, comprising applying a flow body containing a metal powder of a nanometer size and a dispersant to a support (A), firing the metal layer (B'), and removing the metal layer (B); The organic compound containing a dispersing agent in B') forms a void and is formed into a porous metal layer (B), and then the metal layer (C) is formed by electrolysis or electroless plating. The method for producing a laminate according to the seventh aspect of the invention, wherein the nano-sized metal powder has a particle shape or a fibrous shape. The method for producing a laminate according to the seventh aspect of the invention, wherein the nano-sized metal powder is silver, and the metal layer (C) is a copper-plated layer formed by electrolytic copper plating.