JP5660368B2 - Manufacturing method of substrate with Cu pattern and substrate with Cu pattern obtained thereby - Google Patents

Description

  The present invention relates to a method for manufacturing a substrate with a Cu pattern for forming a Cu pattern on a substrate by a coating method or a printing method, and a substrate with a Cu pattern obtained by using the manufacturing method.

Metallic copper has high electrical conductivity and thermal conductivity, and is widely used as a conductor wiring material, a heat transfer material, a heat exchange material, and a heat dissipation material.
On the other hand, since inkjet, jet dispenser, needle dispenser, dispenser, and plate printing can apply liquid materials in any shape without using a photoresist process, on-demand production, labor saving, material saving, and cost reduction It is attracting attention from a point. In particular, inkjet and jet dispensers that can be formed in a non-contact manner can print on steps, curved surfaces, and small areas, and can form patterns that are impossible with plate printing.
Conventionally, a dispersion of copper nanoparticles has been proposed for such a purpose, but there are problems with the low adhesion of the produced conductor layer and the peeling and brittleness of the treated printed layer. It could not be applied to heat transfer materials, heat exchange materials, and heat dissipation materials.
The cause of low adhesion and peeling of the treated printed layer is the porous sintered body in which the metal element-containing particles in the printing ink are sintered. The vulnerability of the porous sintered body and the gap between the printed layer and the substrate This is because the generation of voids and the bonding between the printed layer and the substrate do not occur, and the adhesiveness cannot be obtained. To deal with such problems, conventionally, a polyimide precursor is used as a base resin and a conductor ink is printed thereon (see, for example, Patent Document 1), or a conductor ink is printed on a semi-cured epoxy resin (special feature). (Application No. 2008-267400), a method has been proposed in which a resin as a base is made to have fluidity so as to follow the conductor layer to obtain adhesion, but there are restrictions on the base resin material and the manufacturing method.
Moreover, as a printing ink for forming a metallic copper pattern by such printing, a dispersion of metallic copper nanoparticles or a solution or dispersion of a metal complex has been proposed. However, copper has a stable oxidation state at room temperature (25 ° C.) and always contains copper atoms in the oxidation state. Therefore, copper atoms in the oxidation state are reduced in order to exhibit conductor and heat conductivity as metal copper, and further, copper metal It is necessary to make it a continuum.
As a reduction technique, a reduction technique using formic acid gas is known. As a reduction method using formic acid gas, it has been reported that a formic acid reflow furnace is effective in removing an oxide film on the surface of copper and solder (for example, see Patent Document 2). In recent years, a method of applying this reducing power of formic acid as a method for making a conductor ink into a conductor has been reported (see, for example, Patent Documents 3, 4, and 5).

JP 2008-200557 A Japanese Patent No. 3373499 Korean Patent No. 100867952 JP 2009-252685 A JP 2010-59535 A

The present inventors have pointed out that formic acid gas treatment of copper oxide particles proceeds via sublimable copper formate (Japanese Patent Application No. 2009-215033). Copper oxide reacts with formic acid to produce copper formate, and copper formate diffuses into a gaseous state due to its sublimation property, and metal Cu is produced by thermal decomposition of copper formate. At this time, a dense metal Cu layer having a shape following the substrate can be formed by the copper formate passing through the gaseous state (FIG. 2). However, when a shape following a simple substrate was formed on the resin substrate, sufficient interaction was not obtained between the resin and the metal Cu layer, and adhesion was not obtained.
An object of this invention is to provide the manufacturing method of the board | substrate with Cu pattern in which the adhesiveness of resin and a metal Cu layer is favorable, and the board | substrate with Cu pattern obtained by it.

As a result of studying the above problems, the present inventors have found that an adhesive force can be obtained by treating the surface of the organic substrate with a strong alkaline aqueous solution. When the cross section of the obtained resin substrate was observed, copper penetration of about 100 nm from the surface of the resin substrate, which was not observed when the substrate was not processed (FIG. 2), was observed (FIG. 1). This is because the surface of the resin substrate is treated with a strong alkaline aqueous solution to reduce the crosslinking density due to cleavage of the resin main chain on the surface and introduce a hydrophilic substituent such as a hydroxyl group, a carboxyl group or a carbonyl group, and sublimate formic acid. After copper penetrates into this layer, it is thermally decomposed to form metallic copper in the resin surface layer, which acts as an adhesive anchor and is considered to have improved adhesive strength.
That is, the present invention for solving the above problems is as follows.
(1) The resin substrate is dipped in a strong alkaline aqueous solution , and the resin substrate is washed with ion-exchanged water or distilled water and dried, and then particles of copper (I) oxide or copper (II) oxide are contained in 95 of all particles. After forming a conductor ink containing a solvent containing a mass% and having a vapor pressure of less than 1.34 × 10 ³ Pa at 25 ° C. by coating or printing, heating to 120 ° C. or more in a gas atmosphere containing formic acid A method for manufacturing a substrate with a Cu pattern, which is characterized.
After the resin substrate is treated with a strong alkaline aqueous solution, it is preferable to treat and dry the resin substrate.
(2) The manufacturing method of the board | substrate with Cu pattern as described in said (1) whose strong alkali aqueous solution is either an alkali metal hydroxide, an alkaline earth metal hydroxide, or a metal alkoxide .
(3 ) Coating or printing is selected from the group consisting of inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing, dispenser, needle dispenser, comma coater, slit coater, die coater, and gravure coater. The manufacturing method of the board | substrate with Cu pattern as described in said (1) or ( 2 ) which is any 1 type or more.
( 4 ) The method for producing a substrate with a Cu pattern according to any one of (1) to ( 3 ), wherein the resin substrate is a substrate made of an organic resin material that undergoes a hydrolysis reaction in a strong alkaline aqueous solution.
( 5 ) The resin substrate is made of an organic resin material, and the organic resin material is an epoxy resin, an isocyanate resin, a polyimide resin, a phenol resin, a resole resin, a polyamide resin, a polyamideimide resin, a polyurethane resin, a polycarbonate resin, a polyester resin, The manufacturing method of the board | substrate with Cu pattern in any one of said (1) thru | or (4) which is either urea resin .
( 6) A substrate with a Cu pattern obtained by the method for producing a substrate with a Cu pattern according to any one of (1) to ( 5 ).
(7) The Cu pattern-attached substrate as described in ( 6 ) above, wherein in the cross-sectional observation of the obtained Cu pattern-provided substrate, the adhesion between the Cu pattern and the resin substrate is measured by CYCAS (SAICAS (Surface And Interfacial Cutting Analysis System)) measurement. A Cu-patterned substrate characterized in that the penetration of copper is observed at a depth of 5 nm or more and 300 nm or less from the interface with the Cu pattern in the resin substrate with a property of 0.3 kN / m or more.

  A substrate with a Cu pattern obtained by the method for producing a substrate with a Cu pattern of the present invention provides a substrate with good adhesion between a resin and a metal Cu layer, and can be formed by applying or printing a conductive ink.

FIG. 5 is a drawing-substituting photograph showing a scanning ion microscope image (SIM image) (tilt 45 °) of a focused ion beam (FIB) processed cross section of a resin substrate with a metal copper film produced in Example 1. FIG. (Drawing substitute photograph which shows the SIM image (45 degrees of inclination) of the FIB process cross section of the resin substrate with a metal copper film produced in the comparative example 1.

<Immersion treatment in strong alkaline aqueous solution>
As a method of treating with a strong alkaline aqueous solution used in the method for producing a substrate with a Cu pattern of the present invention, an immersion treatment in a strong alkaline aqueous solution is preferable. In the method for producing a substrate with a Cu pattern according to the present invention, the resin substrate surface is partially hydrolyzed by immersing the resin substrate in a strong alkaline aqueous solution, and a conductive ink containing copper element-containing particles thereon (copper oxidation) It is characterized in that a particle deposition layer (mainly composed of physical particles) is patterned by coating or printing, and the particle deposition layer is treated with gaseous formic acid heated at 120 ° C. or higher.
In the strong alkaline aqueous solution treatment of the resin substrate used in the present invention, the main chain of the resin constituting the resin substrate surface is partially hydrolyzed so that the crosslink density and intermolecular packing are sparse, and the parent metal ionic substituent A surface layer into which is introduced is formed. In the subsequent gaseous formic acid treatment, the sublimated and gasified copper formate permeates and decomposes into the resin surface layer formed by the strong alkaline aqueous solution treatment, and metallic copper is deposited in the resin surface layer, and copper is added to the resin. Is formed, and the adhesion of the Cu film formed thereon is developed.
The substrate that satisfies this requirement, the strong alkaline aqueous solution, the processing conditions, the cleaning (ion-exchange water and distilled water cleaning step), and the drying of the substrate will be described together.

(Resin substrate)
The resin substrate used in the present invention is preferably a substrate made of an organic resin material in order to modify the resin substrate surface by treating with a strong alkaline aqueous solution. As the organic resin material, an organic resin material having hydrolyzability by contact with a strong alkaline aqueous solution can be applied. For example, as such an organic resin material, epoxy resin, isocyanate resin, phenol resin, resol resin, polyimide resin, polyamide Preferred examples include resins, polyamideimide resins, polyurethane resins, polycarbonate resins, polyester resins, and urea resins. In addition to these single organic resin material substrates, resin substrates include inorganic filler filling, cloth impregnated epoxy resin / glass cloth, polyester resin / glass cloth / glass cloth, polyimide resin / glass cloth, etc. Organic / inorganic composite resin substrates may also be used.

(Strong alkaline aqueous solution)
As the type of strong alkali in the strong alkaline aqueous solution used in the present invention, a substance exhibiting strong alkalinity can be used as the aqueous solution. For example, alkali metal and alkaline earth metal hydroxides, metal alkoxides and the like are preferable. It is done. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide and potassium hydroxide, and examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide and barium hydroxide. . Further, tetraalkylammonium hydroxide such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used alone or in combination. Examples of the metal alkoxide include sodium methoxide, sodium ethoxide, potassium butoxide and the like.

(Processing conditions)
The concentration of the strong alkaline aqueous solution is desirably adjusted based on the degree of formation of the surface treatment layer of the resin substrate. The degree of formation of the surface treatment layer is affected not only by the concentration of the strong alkaline aqueous solution, but also by the type of substrate, the type of alkali, the treatment temperature, and the treatment time, so the optimum concentration differs for each system. It is desirable to adjust the type of alkali, the concentration of the strong alkaline aqueous solution, the processing temperature, and the processing time in accordance with the type of substrate. When the processing strength is too strong, the resin is reduced and a resin fragile layer is formed due to the corrosion of the resin, which causes deformation of the resin substrate, deterioration of migration characteristics, and reduction of the adhesive strength of the Cu film. On the contrary, when the processing strength is low, the expression of adhesive force cannot be obtained. The strong alkaline aqueous solution means an alkaline aqueous solution having a concentration capable of exhibiting an adhesive force when the surface treatment of the resin substrate is performed. This adhesive strength is such that it cannot be removed by rubbing with a finger, and preferably the adhesion between the Cu pattern and the resin substrate is 0.3 kN / m or more. In the case of metal alkoxide, it is not necessary to be an aqueous solution.

Water washing (ion exchange water, distilled water washing process)
If the alkali metal ions or alkaline earth metal ions used in the immersion treatment in a strong alkaline aqueous solution remain on the substrate, it will not only cause corrosion of the Cu film, but also electromigration even when used in small quantities. Cause. Therefore, it is preferable to perform washing using water with less ionic impurities such as ion-exchanged water or distilled water after the immersion treatment in the strong alkaline aqueous solution. As washing methods, water washing, running water washing, ultrasonic washing, running water type ultrasonic washing, boiling, jet washing, and mixed jet washing can be used. Moreover, you may wash with water, after neutralizing with an acidic solution.

(Dry substrate)
The resin substrate treated with the strong alkaline aqueous solution is preferably dried after being washed with water. Drying is performed by air drying, hot plate, hot air dryer, thermostatic bath, dry nitrogen stream, dry air stream, infrared heating, electromagnetic wave heating, or the like.

<Application or printing of conductor ink containing copper element-containing particles>
(Conductor ink containing copper element-containing particles)
The conductor ink containing the copper element-containing particles used in the present invention needs to react with formic acid in the formic acid gas treatment described later to produce sublimable copper formate, and therefore contains copper oxide particles as an essential component. Moreover, it is preferable to include the solvent whose vapor pressure in 25 degreeC is less than 1.34 * 10 < ³ > Pa from a printable viewpoint.
The Cu ink for inkjet printing needs to be dispersed so that the average dispersed particle size is 500 nm or less and the maximum dispersed particle size is 2 μm or less.

(Copper oxide particles)
It is preferable that the copper oxide particles contain 95% by mass or more of particles made of copper (I) oxide [cuprous oxide] or copper (II) oxide [cupric oxide] in all particles. The copper oxide particles used in the present invention preferably have a primary particle number average particle size of 1 to 1,000 nm, more preferably 1 to 500 nm, and even more preferably 10 to 100 nm. . For example, commercially available products such as copper oxide nanoparticles produced by the vapor phase evaporation method manufactured by CI Kasei Co., Ltd. and copper oxide nanoparticles synthesized by the plasma flame method produced by Nissin Engineering Co., Ltd. It may be used.

(dispersion)
Dispersion includes ultrasonic dispersers, media dispersers such as bead mills, cavitation stirrers such as homomixers and silverson stirrers, opposed collision methods such as artemizers, and ultra-thin high-speed rotating systems such as Claire SS5 (M Technique Co., Ltd.) It can be carried out using a disperser, a rotating / revolving mixer, or the like.

(solvent)
As the solvent, it is preferable to use a solvent having a vapor pressure at 25 ° C. of less than 1.34 × 10 ³ Pa, preferably less than 1.0 × 10 ³ Pa · s.
Examples of such a solvent include those shown below. That is, aliphatic hydrocarbon solvents such as nonane, decane, dodecane, and tetradecane; aromatic hydrocarbon solvents such as ethylbenzene, anisole, mesitylene, naphthalene, cyclohexylbenzene, diethylbenzene, phenylacetonitrile, phenylcyclohexane, benzonitrile, and mesitylene; Ester solvents such as isobutyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, glycol sulfite, ethyl lactate, methyl lactate; alcohol solvents such as 1-butanol, cyclohexanol, α-terpineol, glycerin; Ketone solvents such as cyclohexanone, 2-hexanone, 2-heptanone, 2-octanone, 1,3-dioxolan-2-one, 1,5,5-trimethylcyclohexen-3-one; Glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate , Diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, Alkylene glycol solvents such as reethylene glycol isopropyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol-t-butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether; dihexyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy Ether solvents such as toluene and benzyl ethyl ether; carbonate solvents such as propylene carbonate and ethylene carbonate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as malononitrile Examples of the solvent are: Among these, γ-butyrolactone, N-methylpyrrolidone, glycol sulfite, and propylene carbonate are preferable. These solvents can be used alone or in combination of two or more.

In addition, in the Cu ink for ink jet printing of the present invention, it is preferable to use it dispersed so that the average dispersed particle diameter is 500 nm or less and the maximum dispersed particle diameter is 2 μm or less. When the average dispersed particle size exceeds 500 nm, the printability and the resistance expression stability are not sufficient. For example, when ejecting by the ink jet printing method, clogging of the ink jet head nozzle or the like occurs, and it becomes impossible to print stably. In addition, when Cu ink is used in an offset printing method or the like, the printed matter is blurred. In order to further improve the printability and the stability of resistance development, the average dispersed particle size of the particles is preferably 300 nm or less. The average dispersed particle size is preferably small, but the lower limit is usually about 5 nm. Furthermore, from the same viewpoint, the maximum dispersed particle size of the particles is preferably 2 μm or less, and more preferably 1 μm or less.
Here, the average dispersed particle size and the maximum dispersed particle size are measured by a photon correlation method based on a dynamic light scattering method using Brownian motion of particles. The average dispersed particle size and the maximum dispersed particle size can be measured using, for example, “Submicron Particle Analyzer N5 Type” (trade name) manufactured by Beckman Coulter.

The Cu ink for ink jet printing used in the present invention has a dynamic viscosity at 25 ° C. of 5 mPa · s or more, preferably 100 mPa · s or less, and more preferably 50 mPa · s or less. If it is less than 5 mPa · s, it may be ejected in the form of a mist at the time of ejection from an inkjet nozzle, or it may flow after being deposited on the substrate and keep the printed shape. Moreover, when it exceeds 100 mPa * s, discharge becomes impossible. The “dynamic viscosity at 25 ° C.” is, in other words, the shear viscosity at a measurement temperature of 25 ° C. and a shear rate of 10 s ⁻¹ .

(Printing or coating method)
The printing method used for the patterning of the conductor ink (Cu ink) may be any method that allows Cu ink to adhere to an arbitrary place. Examples of such methods include inkjet printing, super inkjet printing, screen printing, transfer printing, Offset printing, jet printing method, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, relief printing, intaglio printing, gravure printing, soft lithography, dip pen lithography, particle deposition method, spray coater, spin coater, Dip coater and electrodeposition coating can be used. Among them, inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing method, dispensing Needle dispenser Kanmakota, slit coater, die coater, and any one or more selected from the group consisting of a gravure coater are preferred.

<Cu substrate evaluation method with Cu pattern>
(Adhesiveness)
For the adhesion between the Cu pattern of the substrate with a Cu pattern and the resin substrate, a tape peeling test or a cross-cut test can be used simply. More preferably, the adhesive strength of the interface is measured by SICAS (Surface And Interfacial Cutting Analysis System. If a good interface is formed, a measured value of 0.3 kN / m or more can be obtained.
A micro cutting device called SAICAS is a technique for performing cutting with a fine and sharp cutting blade while controlling the depth position from the surface, and associating the stress applied to the blade with the physical properties of each constituent single film. This method has the advantage that the adhesion force in the substrate state can be quantitatively evaluated. This can be measured using commercially available, for example, NN-03 manufactured by Daipura Wintes Co., Ltd.

(Cross-section observation of substrate with Cu pattern)
The penetration structure of the metal Cu film can be confirmed by processing a cross section and observing with a scanning ion microscope (SIM), a scanning electron microscope (SEM), or a transmission electron microscope (TEM). As the cross-section processing method, focused ion beam (FIB) processing and cross-section polisher method (CP) processing are preferable.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1
(Resin substrate)
Copper foil of epoxy board (E679FB, manufactured by Hitachi Chemical Co., Ltd.) with low roughened copper foil (F0-WS, manufactured by Furukawa Electric Co., Ltd.) in aqueous solution of ammonium peroxodisulfate (manufactured by Junsei Chemical Co., Ltd., ammonium persulfate) The whole surface was etched, washed with water and dried to obtain a resin substrate.
(Strong alkaline aqueous solution treatment of substrates)
4 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 100 g of ultrapure water (ultra pure water production apparatus PRO-0250, FPC-0500, manufactured by Organo Corporation) to prepare a 1 mol / L aqueous solution. Sodium hydroxide was poured into a 200 mL beaker and adjusted to a liquid temperature of 70 ° C. with a water bath. The aforementioned resin substrate was immersed in this aqueous sodium hydroxide solution for 10 minutes. Then, the ultrapure water was replaced with a new one for 10 minutes in 1 L of ultrapure water and washed by immersing 3 times. After cleaning, the substrate was dried with a hot air dryer (safety oven SPH-201, manufactured by Espec Co., Ltd.) at 110 ° C. for 30 minutes to give a substrate treated with a strong alkaline aqueous solution.

(Preparation of Cu ink)
For Cu ink, 40 g of CuO nanoparticles (average particle size 70 nm, manufactured by C-I Kasei Co., Ltd.) were weighed into a plastic bottle, and 4-methyl-1,3-dioxolan-2-one (Wako Pure Chemical Industries, Ltd.) was used as a dispersion medium. 60 g) and 19.6 kHz, 600 W for 5 minutes using an ultrasonic homogenizer (US-600, manufactured by Nippon Seiki Co., Ltd.).

(Preparation of Cu ink application sample)
The Cu ink was dropped onto the substrate treated with the strong alkaline aqueous solution, and applied with a Baker applicator (YBA type, manufactured by Yoshimitsu Seiki Co., Ltd.) adjusted to a gap of 100 μm. Then, after naturally drying for 6 hours, it placed on the hotplate heated at 160 degreeC, and it dried for 30 minutes, and obtained the Cu ink application | coating sample which formed the copper-type particle deposition layer.

(Formic acid treatment)
A formic acid gas generator was prepared by putting formic acid into a washing bottle and bubbling nitrogen. The coated sample was set on a flat bottom separable flask heated in an oil bath with a 5 mm thick glass plate on it. A chromel alumel thermocouple was set on the same glass substrate as the sample, and the processing temperature was measured. Nitrogen containing formic acid gas generated by a formic acid gas generator after the temperature of the glass substrate becomes constant (170 ° C.) by heating in a separable flask in which this sample is set while flowing nitrogen in a 195 ° C. oil bath. Gas was passed through the separable flask at 0.3 L / min, and the copper-based particle deposition layer was treated for 60 minutes. After the treatment, the formic acid gas generator was removed, and the separable flask was allowed to cool while flowing nitrogen, and after the sample became 50 ° C. or lower, the sample was taken out into the air. A substrate with a Cu pattern was produced as described above.

(Characteristic evaluation)
As for the adhesive force of the substrate with Cu pattern, after the fragile layer on the surface of the Cu pattern was scraped with a cloth, a tape peeling test was performed. As a result, the adhesion of the dense layer at the bottom was good. Further, using a SAICAS device (DN-20, Daipura Wintes Co., Ltd.), the cutting speed is 1 μm / second, the cutting width is 500 μm, and the depth is a condition that becomes an interface between the Cu pattern and the substrate. As a result of measuring the adhesive force at the pattern interface, the value was 0.32 kN / m.
Scanning ion microscope image (SIM image) observation of a focused ion beam (FIB) processed cross section was performed, and 100 nm copper penetration from the substrate surface was confirmed (FIG. 1).

(Comparative Example 1)
(Resin substrate), (Preparation of Cu ink), (Preparation of Cu ink-coated sample), and (Formic acid gas treatment) were performed in the same manner as in Example 1 except that the substrate was not subjected to the alkaline aqueous solution treatment.
(Characteristic evaluation)
The adhesive strength of the substrate with the Cu pattern was peeled off when the fragile layer on the surface of the Cu pattern was scraped with a cloth.
Observation of the scanning ion microscope (SIM) image of the FIB processed cross section was carried out in the same manner as in Example 1, but no penetration of copper from the substrate surface was observed (FIG. 2).

1. FIB protective layer (tungsten)
2. 2. Cu ink layer treated with formic acid gas 3. Cu-penetrating epoxy resin substrate surface layer Epoxy resin substrate

Claims (7)

After immersing the resin substrate in a strong alkaline aqueous solution, washing the resin substrate with ion-exchanged water or distilled water and drying, 95% by mass or more of particles made of copper oxide (I) or copper (II) oxide in all particles A conductive ink containing a solvent having a vapor pressure of less than 1.34 × 10 ³ Pa at 25 ° C. is formed by coating or printing, and then heated to 120 ° C. or higher in a gas atmosphere containing formic acid. Manufacturing method of substrate with Cu pattern.   The method for producing a substrate with a Cu pattern according to claim 1, wherein the strong alkaline aqueous solution is one of an alkali metal hydroxide, an alkaline earth metal hydroxide, or a metal alkoxide.   Application or printing is any one selected from the group consisting of inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing, dispenser, needle dispenser, comma coater, slit coater, die coater, and gravure coater. It is a seed | species or more, The manufacturing method of the board | substrate with Cu pattern of Claim 1 or Claim 2.   The method for producing a substrate with a Cu pattern according to any one of claims 1 to 3, wherein the resin substrate is a substrate made of an organic resin material that undergoes a hydrolysis reaction in a strong alkaline aqueous solution. The resin substrate is made of an organic resin material, and the organic resin material is an epoxy resin, isocyanate resin, polyimide resin, phenol resin, resol resin, polyamide resin, polyamideimide resin, polyurethane resin, polycarbonate resin, polyester resin, urea resin. The method for producing a substrate with a Cu pattern according to any one of claims 1 to 4 , which is any one of the above.   The board | substrate with Cu pattern obtained by the manufacturing method of the board | substrate with Cu pattern in any one of Claim 1 thru | or 5.   7. A substrate with a Cu pattern according to claim 6, wherein in the cross-sectional observation of the obtained substrate with the Cu pattern, adhesion between the Cu pattern and the resin substrate is 0 by CYCUS (Surface And Interfacial Cutting Analysis System) measurement. A substrate with a Cu pattern, wherein penetration of copper is observed at a depth of 5 nm or more and 300 nm or less from the interface with the Cu pattern in the resin substrate at 3 kN / m or more.

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