JP2014138051A - Substrate for forming conductive pattern, conductive pattern-formed substrate, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for forming a conductive pattern capable of improving adhesion between the substrate and the conductive pattern, a conductive pattern-formed substrate, and a method for manufacturing the conductive pattern-formed substrate.SOLUTION: A metal thin film 2 with a level of exhibiting no conductivity (non-conductive level) is formed by means of conventional methods including a vacuum deposition method, a sputtering method, an ion plating method or the like so that the mass per unit area of nickel, chromium or an alloy thereof is 4 μg/cmor more and less than 50 μg/cm, preferably, 4 μg/cmor more and less than 20 μg/cm, on a surface of a substrate 1 comprising a resin such as polyethylene terephthalate. When an ink composition containing metal particles or metal oxide particles is printed in a predetermined pattern shape 3P on the metal thin film, and then converted into a conductive pattern 3 with light irradiation, the metal thin film functions as a layer for improving adhesion between the metal or metal oxide particles and the substrate 1.

Description

  The present invention relates to a conductive pattern forming substrate, a conductive pattern forming substrate, and a manufacturing method thereof.

  In order to form a conductive layer such as a semiconductor or a metal on a substrate, for example, an ink layer having a predetermined pattern is printed on the substrate using an ink composition (conductive ink) in which conductive particles are dispersed, It is conceivable to sinter the conductive particles in the ink layer into a conductive pattern.

  For example, in the following Patent Document 1, an adhesive is applied to a substrate to coat an adhesive layer, a substrate coated with the adhesive layer is coated with a water repellent layer, and the substrate coated with the adhesive layer and the water repellent layer is coated. A technique for printing a conductive ink, sintering the printed conductive ink, and curing the adhesive layer is disclosed.

  Further, in Patent Document 2 below, metal fine particles are dispersed from a base material provided with an insulating pattern formed of a thermosetting resin so that the metal fine particles adhere to the insulating pattern, and the insulating pattern is heated. An apparatus is disclosed in which an electronic component is manufactured by melting and fixing the fine metal particles on an insulating pattern, and removing the fine metal particles adhering to the surface of a substrate other than the insulating pattern.

  In the method of Patent Document 1, the sintering condition is heating for 1 hour at 200 ° C. (paragraph 0044 of Patent Document 1), and in the method of Patent Document 2, the heating temperature of the insulating pattern is 150 to 200 ° C. ( In the case of heating a conductive pattern or an insulating pattern on a substrate, generally, the substrate that can be used has high heat resistance, such as a bismaleimide triazine compound. It is limited to high heat-resistant thermosetting resins such as BT resin.

  Further, in Patent Document 3 below, when a conductive pattern is formed from a fluid electrode material such as a conductive paste, an adhesive layer that enhances the adhesion of the conductive layer to the substrate is formed on the substrate in the above pattern, A technique is disclosed in which a conductive paste is roughly deposited on a substrate, heated and dried to form a conductive layer, and then the conductive layer is left only on the adhesive layer by ultrasonic cleaning or the like.

  In Patent Document 3, the temperature of the heating and drying step is about 80 ° C. (paragraph 0188 of Patent Document 3), but it is described that heating is performed at 100 to 300 ° C. in order to thermally fuse the metal fine particles. As in Patent Documents 1 and 2, there is a problem that the material of the substrate that can be used is limited.

  Therefore, as described in Patent Documents 4 to 6, there has been an attempt to convert to a metal wiring by light irradiation or microwave heating using an ink composition containing particles such as nanoparticles. In the method using light energy or microwave for heating, only the ink composition (conductive composition) can be heated, and there is a possibility that a resin having a heat resistant temperature lower than the above resin can be used for the substrate.

JP 2010-75911 A JP 2005-203396 A JP 2008-159971 A Special table 2008-522369 International Publication 2010/110969 Pamphlet Special table 2010-528428 gazette

However, in the conventional sintering technique by light irradiation, particles such as metal particles or metal oxide particles contained in an ink composition (conductive composition) which is a material for forming a conductive pattern at the time of light irradiation Since the adhesion to the substrate is poor, there is a problem that the particles are peeled off from the substrate surface and a conductive pattern cannot be formed on the substrate. This phenomenon is prominent when, for example, silver or copper or copper oxide is used as the particles, and a resin such as polyethylene terephthalate is used as the substrate. In this specification, the conductive pattern is a metal in the binder resin. Conductive conductivity containing metal formed in a pattern as a result of sintering metal particles or metal oxide particles by forming an ink composition in which particles or metal oxide particles are dispersed into a printed pattern and irradiating it with light A conductive layer that is a metal thin film.

  It is an object of the present invention to improve the adhesion between a substrate and metal particles or metal oxide particles through a non-conductive layer containing metal by forming a non-conductive layer containing metal between the substrate and the conductive pattern. , A conductive pattern forming substrate capable of improving the adhesion between the substrate and the conductive pattern by suppressing the peeling of the metal particles or metal oxide particles during sintering by light irradiation, and the conductive pattern forming substrate, It is also intended to provide a manufacturing method thereof.

  In order to achieve the above object, an embodiment of the present invention is a conductive pattern forming substrate, comprising: a substrate; and a non-conductive layer including a metal formed on at least one main surface of the substrate. It is characterized by that.

In another embodiment of the present invention, there is provided a conductive pattern forming substrate, the substrate and an ink composition containing metal particles or metal oxide particles formed on at least one main surface of the substrate. And a non-conductive layer containing a metal that improves the adhesion of the conductive pattern produced by irradiating the printed pattern printed in the pattern shape to the substrate. Here, the mass per unit area of the metal constituting the non-conductive layer containing the metal is preferably 4 μg / cm ² or more and less than 50 μg / cm ² , and the unit area of the metal constituting the non-conductive layer containing the metal The hit mass is more preferably 4 μg / cm ² or more and less than 20 μg / cm ² .

  The metal constituting the non-conductive layer containing the metal is preferably made of nickel or chromium or an alloy containing them, and the substrate is made of polyester, polycarbonate, polyacrylate, polyolefin, cycloolefin polymer. , Polyimide, epoxy, fluorinated ethylene propylene, polyether ether ketone, polyethylene tetrafluoroethylene, polyetherimide, polytetrafluoroethylene, polyvinyl chloride, silicon, glass, paper or non-woven fabric. Is preferred. In particular, the polyester is preferably polyethylene terephthalate (PET).

  Further, it is preferable that the substrate is a transparent substrate and the total light transmittance is 60% or more.

  Still another embodiment of the present invention is a conductive pattern forming substrate, wherein a conductive pattern including a metal is formed on a nonconductive layer including a metal of the conductive pattern forming substrate. To do.

Still another embodiment of the present invention is a method of manufacturing a conductive pattern forming substrate, wherein a thin metal layer is formed on at least one main surface of the substrate by a vacuum deposition method, a sputtering method, or an ion plating method. A non-conductive layer containing metal is formed. Here, the mass per unit area of the metal constituting the non-conductive layer containing the metal is preferably 4 μg / cm ² or more and less than 50 μg / cm ² , and the unit area of the metal constituting the non-conductive layer containing the metal The hit mass is more preferably 4 μg / cm ² or more and less than 20 μg / cm ² .

  The metal constituting the non-conductive layer containing metal is preferably made of nickel or chromium or an alloy containing them, and the substrate is made of polyester, polycarbonate, polyacrylate, polyolefin, cycloolefin polymer, polyimide, It is preferably composed of epoxy, fluorinated ethylene propylene, polyether ether ketone, polyethylene tetrafluoroethylene, polyetherimide, polytetrafluoroethylene, polyvinyl chloride, silicon, glass, paper or non-woven fabric. . In particular, the polyester is preferably polyethylene terephthalate.

  Further, it is preferable that the substrate is a transparent substrate and the total light transmittance is 60% or more.

  Yet another embodiment of the present invention is a method for manufacturing a conductive pattern forming substrate, wherein the conductive pattern forming substrate manufactured by the method for manufacturing a conductive pattern forming substrate is formed on a non-conductive layer containing a metal. A step of forming a print pattern by printing an ink composition containing metal particles or metal oxide particles in a binder resin in a predetermined pattern shape; and irradiating the print pattern with light to form metal particles or metal oxide particles. And a step of forming a conductive pattern containing a metal by sintering.

  In the present specification, the “conductive pattern forming substrate” means a substrate on which a conductive pattern is not formed (before the conductive pattern is formed), and the “conductive pattern formed substrate” is formed with a conductive pattern ( It means the substrate (after the formation of the conductive pattern).

  According to the present invention, the non-conductive layer containing metal is formed between the substrate and the conductive pattern, thereby improving the adhesion between the substrate and the metal particles or metal oxide particles through the non-conductive layer containing metal. The conductive pattern can be reliably formed on the substrate while suppressing the metal particles or the metal oxide particles from being peeled off during sintering by light irradiation.

It is a figure which shows the manufacturing process of the board | substrate for conductive pattern formation concerning embodiment, and a conductive pattern formation board | substrate. It is a figure for demonstrating the definition of pulsed light.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments) will be described with reference to the drawings.

  1A to 1F show a conductive pattern forming substrate and a manufacturing process of the conductive pattern forming substrate according to the embodiment. In FIG. 1, each process is shown by sectional drawing. In the example of this manufacturing process, the substrate 1 shown in FIG. 1A is prepared, and as shown in FIGS. 1B and 1C, at least one main surface of the substrate 1 is vacuum deposited or sputtered. The non-conductive layer 2 containing a metal is formed by an existing method such as a method or an ion plating method. Thereby, the board | substrate for conductive pattern formation which has the board | substrate 1 and the nonelectroconductive layer 2 containing the metal formed in the at least one main surface of the board | substrate 1 is manufactured.

  In addition, an ink composition in which metal particles or metal oxide particles are dispersed in a binder resin is formed on a main surface of the non-conductive layer 2 containing metal opposite to the substrate 1 with a predetermined pattern shape (solid pattern). And the conductive pattern 3 is formed by sintering by light irradiation. Thereby, a conductive pattern forming substrate is manufactured. A method of manufacturing the conductive pattern forming substrate on which the conductive pattern 3 is formed will be described later.

  Materials used for the substrate 1 include polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyacrylate, polyolefin, cycloolefin polymer, polyimide, epoxy, fluorinated ethylene propylene, polyether ether ketone, polyethylene tetrafluoro. Examples of the material include a resin formed of a resin such as ethylene, polyetherimide, polytetrafluoroethylene, and polyvinyl chloride, silicon, glass, paper, or non-woven fabric, but the material is not limited to these, and is a material that can be used as a substrate. I just need it. The thickness of the substrate is preferably 10 μm to 3 mm. If the thickness of the substrate is too thin, it is not preferable because the strength of the substrate is lost. The thicker one is not particularly limited, but if the flexibility is required, a too thick one cannot be used. Therefore, the thickness of the substrate is preferably 10 μm to 3 mm, more preferably 16 μm to 288 μm in consideration of flexibility and availability.

  The non-conductive layer 2 containing a metal is a thin film containing a metal. However, in order for the conductive pattern 3 formed on the non-conductive layer 2 containing a metal to function as an electronic circuit pattern, the non-conductive layer containing a metal is used. There should be no short circuit between 2 and the conductive pattern 3. Therefore, it must be non-conductive rather than conductive.

Moreover, as a material used for the non-conductive layer 2 containing the above metal, a metal such as nickel, chromium, cobalt, aluminum, tin, zinc, or an alloy containing these can be used, and among these, nickel or chromium or an alloy containing them is used. It can be preferably used. As described above, the non-conductive layer 2 containing a metal has conductivity of these metals on at least one main surface of the substrate 1 by an existing method such as a vacuum deposition method, a sputtering method, or an ion plating method. It is formed as a thin layer with a level that does not develop (non-conductive). When the metal is formed as a thin layer by the above method, it may not be formed as a thin film having a uniform film thickness, but may be formed in a sea-island shape microscopically. The “non-conductive layer containing a metal” includes the case where it is formed in a sea-island shape in this way. Since it is difficult to measure the exact film thickness of the non-conductive layer 2 containing a metal, the mass of the metal formed per unit area can be used as a parameter corresponding to the film thickness. The mass per unit area of the metal constituting the non-conductive layer 2 containing a metal is 4 μg / cm ² or more and less than 50 μg / cm ² , preferably 4 μg / cm ² or more and less than 20 μg / cm ² . When a transparent substrate such as polyethylene terephthalate, polyethylene naphthalate, or cycloolefin polymer is used, the total light transmittance can be used as a parameter corresponding to the film thickness. When a transparent substrate is used, the value of the total light transmittance of the conductive pattern forming substrate is preferably 60% or more. The “transparent substrate” means a substrate having a total light transmittance of 85% or more. The upper limit value of the total light transmittance corresponds to the total light transmittance of the substrate 1 itself.

If the mass per unit area of the metal constituting the non-conductive layer 2 containing metal is 50 μg / cm ² or more, or if the total light transmittance is less than 60%, the appearance of the substrate is impaired, and the metal The conductive pattern 3 formed on the non-conductive layer 2 containing metal may not function as an electronic circuit pattern because the non-conductive layer 2 is electrically conductive and a short circuit occurs. Further, when the value of the total light transmittance is the upper limit value, it means that the non-conductive layer 2 containing metal is not formed on the main surface of the substrate 1.

  The non-conductive layer 2 containing metal may be formed on the entire surface of at least one main surface of the substrate 1 or may be formed on a part of the main surface, for example, a region where the conductive pattern 3 is formed. .

  Next, the manufacturing method of the conductive pattern formation board | substrate with which the conductive pattern 3 was formed is demonstrated. In order to form the conductive pattern 3 on the main surface of the conductive pattern forming substrate according to the present embodiment (the main surface opposite to the substrate 1 of the nonconductive layer 2 containing metal), the nonconductive layer containing the metal is used. An ink composition in which metal particles or metal oxide particles are dispersed in a binder resin is printed on the substrate 2 in a predetermined pattern shape to form an appropriate print pattern 3p (FIG. 1 (d)). Irradiation is performed (FIG. 1 (e)), and metal particles or metal oxide particles contained in the ink composition are sintered to be converted into the conductive pattern 3 (FIG. 1 (f)). At this time, both the non-conductive layer 2 containing the metal in the portion printed with the ink composition in a predetermined pattern shape and the non-conductive layer 2 containing the metal in the non-printed portion change state before and after the light irradiation. It does not occur. In the case of an ink composition using metal oxide particles, the metal oxide particles are reduced by an appropriate reducing agent contained in the ink composition to form a metal sintered body. Moreover, the printing method of the ink composition is not particularly limited, and for example, printing methods such as inkjet printing, screen printing, offset printing, masking printing, and the like can be used.

  Examples of the material used for the metal particles contained in the ink composition include gold, silver, copper, cobalt, nickel, iron, zinc, indium, and tin. Examples of the material used for the metal oxide particles include copper oxide, cobalt oxide, nickel oxide, iron oxide, zinc oxide, indium oxide, and tin oxide. Among these, copper oxide is more preferable because the reduced metal has high conductivity. The particle size of the metal particles and metal oxide particles used depends on the desired printing accuracy. However, if the particle size is too small, it is difficult to formulate the ink, and the surface area per mass also increases, preventing aggregation. It is necessary to use a relatively large amount of protective colloid used for the purpose. In addition, when the particle size is too large, fine patterns cannot be printed, so that there is a problem that the particles do not contact well and are not easily sintered. Therefore, the particle size is generally selected from 5 nm to 10 μm, more preferably from 10 nm to 5 μm. The particle size was measured with a Nikkiso Microtrac, and the value of D50 was used.

  Further, the binder resin in the ink composition is necessary for printing the ink composition on the non-conductive layer 2 containing a metal. Examples of the polymer compound that can be used as the binder resin include poly-N-vinyl compounds such as polyvinyl pyrrolidone and polyvinyl caprolactone, polyalkylene glycol compounds such as polyethylene glycol, polypropylene glycol, and polyTHF, polyurethanes, cellulose compounds and derivatives thereof, Thermoplastic resins and thermosetting resins such as epoxy compounds, polyester compounds, chlorinated polyolefins, and polyacryl compounds can be used.

  As described above, in the case of an ink composition using metal oxide particles, the metal oxide particles are sintered to form a metal sintered body in order to form a conductive pattern containing metal by light irradiation. (The metal oxide must be reduced to a metal), and for this purpose, it is necessary to include a reducing agent in the ink composition. All have a function as a reducing agent. Among these, polyvinyl pyrrolidone is preferable when considering the binder effect, polyalkylene glycol such as polyethylene glycol and polypropylene glycol is preferable when considering the reducing effect, and a polyurethane compound is preferable from the viewpoint of adhesive strength as a binder. Polyalkylene glycols such as polyethylene glycol and polypropylene glycol fall into the category of polyhydric alcohols, and have particularly suitable properties as reducing agents.

  In addition to the binder resin, an appropriate reducing agent may be added to the ink composition. Reducing agents include alcohol compounds such as methanol, ethanol, isopropyl alcohol, butanol, cyclohexanol, and terpeniol, polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, and carboxylic acids such as formic acid, acetic acid, succinic acid, and succinic acid. , Carbonyl compounds like acetone, methyl ethyl ketone, benzaldehyde, octyl aldehyde, ester compounds like ethyl acetate, butyl acetate, phenyl acetate, hydrocarbon compounds like hexane, octane, toluene, naphthalene, decalin, cyclohexane I can do it. Of these, considering the efficiency of the reducing agent, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, and carboxylic acids such as formic acid, acetic acid and oxalic acid are preferred. The amount of the reducing agent blended is not limited as long as it is an amount necessary for the metal oxide particles, but usually serves as a solvent for the composition containing the binder resin, so that the mass of the metal oxide particles is 100 masses. 5-200 mass parts is mix | blended with respect to a part.

  The light to be irradiated to sinter the metal particles or metal oxide particles contained in the ink composition is preferably continuous light or pulsed light having a wavelength of 200 nm to 3000 nm, and pulsed light that is less likely to store heat during sintering. preferable. In this specification, “pulse light” means light having a short light irradiation period (irradiation time). When light irradiation is repeated a plurality of times, as shown in FIG. 2, the first light irradiation period (on ) And the second light irradiation period (on) means light irradiation having a period (irradiation interval (off)) in which light is not irradiated. Although FIG. 2 shows that the light intensity of the pulsed light is constant, the light intensity may change within one light irradiation period (on). The pulsed light is emitted from a light source including a flash lamp such as a xenon flash lamp. Using such a light source, a pulse light is irradiated onto a pattern in which the composition is printed in a predetermined shape. In the case of repeating irradiation n times, one cycle (on + off) in FIG. 2 is repeated n times. In the case of repeated irradiation, it is preferable to cool from the substrate 1 side so that the conductive pattern forming substrate can be cooled to near room temperature when the next pulse light irradiation is performed.

  The pulse width of the pulsed light, that is, one irradiation period (on), is preferably in the range of 5 μsec to 1 sec, more preferably 20 μsec to 10 msec. If it is shorter than 5 μs, sintering does not proceed and the effect of improving the performance of the conductive pattern 3 is reduced. On the other hand, if the time is longer than 1 second, the adverse effect due to the light deterioration and thermal deterioration of the substrate 1 becomes larger. Irradiation with pulsed light is effective even if performed in a single shot, but can also be performed repeatedly as described above. When it is repeatedly performed, the irradiation interval (off) is preferably in the range of 20 μs to 5 seconds, more preferably in the range of 2 milliseconds to 2 seconds. If it is shorter than 20 μs, it becomes close to continuous light and is irradiated without being allowed to cool after one irradiation, so that the substrate is heated and the temperature becomes considerably high. Also, if it is longer than 5 seconds, the cooling is progressed, so there is no reason for no effect at all. Note that a light source operating at 0.2 Hz or more can be used for the irradiation with the pulsed light. Moreover, as the pulsed light, an electromagnetic wave having a wavelength range of 1 pm to 1 m can be used.

  As described above, the conductive pattern 3 contains a metal. However, in the case of an ink composition using metal oxide particles, the metal oxide particles are completely removed depending on the use of the reducing agent and the irradiation conditions. In some cases, a metal sintered body is not formed, and a part of the metal oxide is included. However, as long as the object of the present invention can be achieved, the conductive pattern 3 in such a state is also included in the conductive pattern 3 including a metal in the present specification.

Since the non-conductive layer 2 containing metal according to the present embodiment has high adhesion to the metal particles or metal oxide particles contained in the ink composition, light for sintering the metal particles or metal oxide particles is used. When irradiating, it can suppress that a metal particle or a metal oxide particle is peeled from the board | substrate for conductive pattern formation (the nonelectroconductive layer 2 containing the metal). As a result, the adhesion between the substrate 1 and the conductive pattern 3 is improved through the nonconductive layer 2 containing metal. For this purpose, the mass per unit area of the non-conductive layer 2 containing metal is preferably set to the above lower limit (4 μg / cm ² ) or more, and when smaller than the lower limit, metal particles or metal oxide particles In some cases, it is not possible to sufficiently obtain the effect of suppressing the peeling.

  Examples of the present invention will be specifically described below. In addition, the following examples are for facilitating understanding of the present invention, and the present invention is not limited to these examples.

Example 1
A polyimide film (Kapton 150EN, manufactured by Toray DuPont Co., Ltd., thickness: 38 μm, total light transmittance: 60.3%) as a substrate in a vacuum vessel of a batch evaporation machine (EVB-6CH, ULVAC, Inc.) Install and deposit the nickel, which is the material to be vapor deposited, on the tungsten board, vaporize the material by applying a voltage by applying a vacuum of 10 ⁻³ to 10 ⁻⁴ torr, and the mass per unit area of the metal (nickel) Was attached to a polyimide film so as to be 9 μg / cm ^2, and a conductive pattern forming substrate of Example 1 in which a nickel layer which is a nonconductive layer containing a metal was formed on the polyimide film was obtained. In addition, the mass per unit area of the metal which comprises the nonelectroconductive layer containing a metal was performed with the following method. First, a 1 cm square conductive pattern forming substrate was immersed in 20 ml of nitric acid (EL nitric acid manufactured by Kanto Chemical Co., Inc.) and heated on a hot plate at 120 ° C. to dissolve the nonconductive layer containing metal. The dissolved solution was recovered to prepare a 50 ml sample solution. Thereafter, the amount of metal in the sample solution was measured using an ICP mass spectrometer (Agilent ICP-MS 7500). The total light transmittance of the obtained substrate for forming a conductive pattern was 57.5%.

  On the nickel layer of the conductive pattern forming substrate obtained in Example 1, a copper oxide ink ICI-020 (NovaCentrix particle size D50 = 200 nm), which is an ink composition, was used for screen printing. A 2 cm × 2 cm square pattern was printed at a thickness of 8 μm to form a printed pattern. The sample thus obtained was subjected to pulse irradiation using Xenon Sinteron 2000 to sinter and reduce the copper oxide particles, thereby converting the printed pattern into a conductive pattern containing copper on the polyimide film. A conductive pattern forming substrate of Example 1 was obtained in which a nickel layer and a conductive pattern containing copper were sequentially formed. Irradiation conditions were as follows: a pulse width of 2000 μsec, a voltage of 3000 V, and an irradiation distance of 4.5 cm. The pulse energy at that time was 2070J.

Example 2
On the nickel layer of the substrate for forming a conductive pattern of the present invention obtained in Example 1, the ink composition silver flake ink HPS-021 (silver particle diameter D50 = 2 μm) manufactured by NovaCentrix was used. A 2 cm × 2 cm square pattern was printed at a thickness of 14 μm by printing to form a printed pattern. The sample thus obtained was subjected to pulse irradiation using Xenon Sinteron 2000 to sinter silver particles, thereby converting the printed pattern into a conductive pattern, a nickel layer on the polyimide film, and silver As a result, a conductive pattern forming substrate of Example 2 in which the conductive patterns including were sequentially formed was obtained. Irradiation conditions were as follows: a pulse width of 2000 μsec, a voltage of 3000 V, and an irradiation distance of 4.5 cm. The pulse energy at that time was 2070J.

Example 3
A polyimide film (Kapton 150EN, manufactured by Toray DuPont Co., Ltd., thickness: 38 μm, total light transmittance: 60.3%) as a substrate in a vacuum vessel of a batch evaporation machine (EVB-6CH, ULVAC, Inc.) Install and deposit chromium, which is the material to be deposited, on a tungsten board, vaporize the material by applying a voltage with a vacuum vessel of 10 ⁻³ to 10 ⁻⁴ torr, and mass per unit area of metal (chromium) Was attached to a polyimide film so as to be 7 μg / cm ^2, and a conductive pattern forming substrate of Example 3 in which a chromium layer, which is a nonconductive layer containing metal, was formed on the polyimide film was obtained. The mass per unit area was measured by the same method as in Example 1. The total light transmittance of the obtained substrate for forming a conductive pattern was 58.2%.
Using the copper oxide ink used in Example 1 on the chromium layer of the conductive pattern forming substrate obtained in Example 3, a conductive pattern was formed in the same manner as in Example 1, and the chromium layer was formed on the polyimide film. And the conductive pattern formation board | substrate of Example 3 in which the conductive pattern containing copper was formed sequentially was obtained.

Example 4
Using the silver flake ink used in Example 2 on the chromium layer of the conductive pattern forming substrate obtained in Example 3, a conductive pattern was formed in the same manner as in Example 2, and the chromium layer was formed on the polyimide film. And the conductive pattern formation board | substrate of Example 4 in which the conductive pattern containing silver was formed in order was obtained.

Comparative Example 1
On the polyimide film used in Example 1, the copper oxide ink used in Example 1 was used, and a conductive pattern was formed in the same manner as in Example 1 (non-containing metal of the conductive pattern forming substrate of Example 1). No conductive layer was formed), and a conductive pattern forming substrate of Comparative Example 1 in which a conductive pattern containing copper was directly formed on a polyimide film was obtained.

Comparative Example 2
On the polyimide film used in Example 1, the silver flake ink used in Example 2 was used, and a conductive pattern was formed in the same manner as in Example 2 (non-containing metal of the conductive pattern forming substrate of Example 2). No conductive layer was formed), and a conductive pattern forming substrate of Comparative Example 2 in which a conductive pattern containing silver was directly formed on a polyimide film was obtained.

  The printed thicknesses of copper oxide ink and silver flake ink, and the results of volume resistivity and adhesion are shown in Table 1.

Examples 5-8
A PET film (Emblet S, manufactured by Unitika Co., Ltd., thickness: 50 μm, total light transmittance: 89.2%) as a substrate in a vacuum vessel of a batch evaporation machine (EVB-6CH, ULVAC, Inc.) The target unit area shown in Table 2 is set and vaporized by applying a voltage by putting nickel, which is a material to be deposited, on a tungsten board, applying a voltage with a vacuum vessel of 10 ⁻³ to 10 ⁻⁴ torr. The conductive pattern forming substrates of Examples 5 to 8 were obtained in which a nickel layer, which is a non-conductive layer containing a metal, was formed on the PET film so as to have a hit mass. The mass of metal (nickel) per unit area was measured by the same method as in Example 1. Table 2 shows the total light transmittance of the obtained conductive pattern forming substrate.

Using the copper oxide ink used in Example 1 on each of the nickel layers of the conductive pattern forming substrates obtained in Examples 5 to 8, conductive patterns were formed in the same manner as in Example 1, and on the PET film. The conductive pattern formation board | substrate of Examples 5-8 by which the nickel layer and the conductive pattern containing copper were sequentially formed in this was obtained.
Examples 9-12

  Using the silver flake ink used in Example 2 on each of the nickel layers of the conductive pattern forming substrate of the present invention obtained in Examples 5 to 8, a conductive pattern was formed in the same manner as in Example 2, The conductive pattern formation board | substrate of Examples 9-12 in which the conductive pattern containing a nickel layer and silver was formed in order on the PET film was obtained.

Examples 13 to 16, Comparative Example 3
A PET film (Emblet S, manufactured by Unitika Co., Ltd., thickness: 50 μm, total light transmittance: 89.2%) as a substrate in a vacuum vessel of a batch vapor deposition machine (EVB-6CH, manufactured by ULVAC, Inc.) Install and deposit chromium, which is the material to be deposited, on a tungsten board, apply a voltage by applying vacuum to the vacuum vessel at 10 ⁻³ to 10 ⁻⁴ torr, and the target unit area shown in Table 2 A conductive pattern forming substrate of Examples 13 to 16 and a conductive pattern forming substrate of Comparative Example 3 in which a chromium layer which is a non-conductive layer containing a metal is formed on the PET film so as to have a hit mass. A substrate was obtained. In addition, the metal (chromium) mass per unit area was measured by the same method as in Example 1. Table 2 shows the total light transmittance of the obtained conductive pattern forming substrate.

  The copper oxide ink used in Example 1 was used on the chromium layer of the conductive pattern forming substrate obtained in Examples 13 to 16 and on the chromium layer of the conductive pattern forming substrate obtained in Comparative Example 3, respectively. Then, the conductive pattern was formed in the same manner as in Example 1, and the conductive pattern forming substrates of Examples 13 to 16 in which the chromium layer and the conductive pattern containing copper were sequentially formed on the PET film, and the conductive of Comparative Example 3 were used. A patterned substrate was obtained.

Examples 17-20, comparative example 4
The silver flake ink used in Example 2 was used on the chromium layer of the conductive pattern forming substrate obtained in Examples 13 to 16 and on the chromium layer of the conductive pattern forming substrate of Comparative Example 3, respectively. Conductive patterns were formed in the same manner as in Example 2, and a conductive pattern forming substrate of Examples 17 to 20 and a conductive pattern forming substrate of Comparative Example 4 in which a chromium layer and a conductive pattern containing silver were sequentially formed on a PET film. Got.
Comparative Example 5

  Using the copper oxide ink used in Example 1 on the PET film used in Examples 5 to 8, a conductive pattern was formed in the same manner as in Example 1 (for the conductive pattern forming substrates of Examples 5 to 8). A non-conductive layer containing metal was not formed), and a conductive pattern-formed substrate of Comparative Example 5 in which a conductive pattern containing copper was directly formed on a PET film was obtained.

Comparative Example 6
On the PET film used in Examples 5 to 8, the silver flake ink used in Example 2 was used, and a conductive pattern was formed in the same manner as in Example 2 (for the conductive pattern forming substrates of Examples 9 to 12). A conductive pattern-formed substrate of Comparative Example 6 in which a conductive pattern containing silver was directly formed on a PET film was obtained.

  The printed thicknesses of copper oxide ink and silver flake ink, and the results of volume resistivity and adhesion are shown in Table 2.

  The volume resistivity of the conductive patterns shown in Tables 1 and 2 above was measured using a Loresta GP manufactured by Mitsubishi Analitech Co., Ltd.

  The total light transmittance of the substrate and the conductive pattern forming substrate was measured using a turbidimeter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) after cutting the substrate or the conductive pattern forming substrate with a 50 mm square.

Moreover, the adhesiveness shown in Table 1 and Table 2 is a mass change rate with respect to the case where the coating film which became the conductive pattern was not peeled off from the substrate by light irradiation. This adhesion is determined by measuring the mass of the coating film before and after light irradiation and calculating the mass reduction of the coating film. When metal oxide particles were used, the calculation was performed in terms of mass when the metal oxide particles were completely converted to metal particles by light irradiation. The notation of the symbol indicating adhesion was defined as follows.
A: Mass change rate 0 to 5%. ○: Mass change rate of 5 to 10%. Δ: Mass change rate of 10 to 15%. X: Mass change rate 15%-. However, each of the above ranges is a lower limit value or more and less than an upper limit value.

  As shown in Table 1, the conductive pattern forming substrate of any of the examples has better adhesion than the conductive pattern forming substrates of Comparative Examples 1 and 2 in which the non-conductive layer containing metal is not formed. Yes.

  In addition, as shown in Table 2, the conductive pattern formation substrate of any of the examples has better adhesion than the conductive pattern formation substrates of Comparative Examples 5 and 6 in which the nonconductive layer containing metal is not formed. doing.

  Moreover, in order to confirm the presence or absence of conduction of the non-conductive layer containing metal, a sheet resistance measurement test of a 2 cm square conductive pattern forming substrate was performed using Loresta GP manufactured by Mitsubishi Analytech Co., Ltd. At that time, it was defined as conducting when a sheet resistance of 20 MΩ / □ or less was observed. In the case of conduction as in Comparative Examples 3 and 4 shown in Table 2, even if the adhesion is good by forming a thick non-conductive layer containing metal, the appearance is impaired in terms of transparency and the metal There is a problem that a short circuit occurs when the non-conductive layer including the conductive layer is conductive, and an electronic circuit pattern cannot be formed.

  1 substrate, 2 non-conductive layer containing metal, 3 conductive pattern.

Claims (13)

A substrate,
A non-conductive layer containing a metal formed on at least one main surface of the substrate;
A conductive pattern forming substrate comprising: A substrate,
A conductive pattern formed on at least one main surface of the substrate and produced by irradiating a printed pattern formed by printing an ink composition containing metal particles or metal oxide particles in a predetermined pattern shape onto the substrate. A non-conductive layer containing a metal that improves adhesion;
A conductive pattern forming substrate comprising: The substrate for forming a conductive pattern according to claim 1 or 2, wherein a mass per unit area of the metal constituting the non-conductive layer containing the metal is 4 µg / cm ² or more and less than 50 µg / cm ² .   4. The conductive pattern forming substrate according to claim 1, wherein a metal constituting the non-conductive layer containing the metal is made of nickel, chromium, or an alloy containing them. 5.   The substrate is polyester, polycarbonate, polyacrylate, polyolefin, cycloolefin polymer, polyimide, epoxy, fluorinated ethylene propylene, polyether ether ketone, polyethylene tetrafluoroethylene, polyetherimide, polytetrafluoroethylene, polyvinyl chloride, silicon The conductive pattern forming substrate according to any one of claims 1 to 4, wherein the conductive pattern forming substrate is made of any one of glass, paper, and nonwoven fabric.   The substrate for forming a conductive pattern according to any one of claims 1 to 5, wherein the substrate is made of a transparent substrate and has a total light transmittance of 60% or more. A conductive pattern forming substrate, wherein a conductive pattern containing metal is formed on a nonconductive layer containing metal of the conductive pattern forming substrate according to claim 1.   A method for producing a substrate for forming a conductive pattern, characterized in that a thin metal layer is formed on at least one main surface of a substrate by a vacuum deposition method, a sputtering method or an ion plating method to form a non-conductive layer containing a metal. . The manufacturing method of the board | substrate for conductive pattern formation of Claim 8 whose mass per unit area of the metal which comprises the nonelectroconductive layer containing the said metal is 4 microgram / cm < ² > or more and less than 50 microgram / cm < ² >.   The method for producing a conductive pattern forming substrate according to claim 8 or 9, wherein the metal constituting the non-conductive layer containing the metal is made of nickel, chromium, or an alloy containing them.   The substrate is polyester, polycarbonate, polyacrylate, polyolefin, cycloolefin polymer, polyimide, epoxy, fluorinated ethylene propylene, polyether ether ketone, polyethylene tetrafluoroethylene, polyetherimide, polytetrafluoroethylene, polyvinyl chloride, silicon The manufacturing method of the board | substrate for conductive pattern formation as described in any one of Claim 8 to 10 comprised by any one of glass, paper, or a nonwoven fabric.   The method for manufacturing a substrate for forming a conductive pattern according to any one of claims 8 to 11, wherein the substrate is formed of a transparent substrate and has a total light transmittance of 60% or more. Metal particles or metal oxide particles on a binder resin on a non-conductive layer containing a metal of a conductive pattern forming substrate manufactured by the method for manufacturing a conductive pattern forming substrate according to any one of claims 8 to 12. Forming a printed pattern by printing an ink composition containing a predetermined pattern shape, and irradiating the printed pattern with light to sinter metal particles or metal oxide particles to form a conductive pattern containing metal And a step of forming the conductive pattern forming substrate.

Images