CN114015278A

CN114015278A - Chemical copper plating photocuring activation ink and preparation method thereof, and preparation method of addition circuit board

Info

Publication number: CN114015278A
Application number: CN202111541894.1A
Authority: CN
Inventors: 符显珠; 丁萍; 林长霖; 罗诗隆; 史希言
Original assignee: Shenzhen University
Current assignee: Shenzhen University
Priority date: 2021-12-16
Filing date: 2021-12-16
Publication date: 2022-02-08
Anticipated expiration: 2041-12-16
Also published as: CN114015278B

Abstract

The invention provides chemical copper plating photocuring activation ink, a preparation method thereof and a preparation method of an addition circuit board, wherein the chemical copper plating photocuring activation ink comprises an organic solvent, a carbon-supported metal nano composite material, a prepolymer monomer, an active diluent monomer, a photoinitiator and an auxiliary agent, wherein the carbon-supported metal nano composite material is dissolved in the organic solvent and consists of carbon black and a metal nanoparticle catalyst. The chemical copper plating photo-curing activation ink prepared by the invention is uniform and stable slurry, and can be sealed and stored at room temperature for one month and still keep the original shape; the chemical copper plating photo-curing activation ink can achieve the effect of complete curing within a few seconds under the condition of ultraviolet illumination, and the production efficiency is greatly improved; the chemical copper plating photo-curing activation ink can also be directly in selective patterning design on a base material, gives flexibility to a circuit, and meets the development of the printed circuit board industry to the field of addition circuit boards.

Description

Chemical copper plating photocuring activation ink and preparation method thereof, and preparation method of addition circuit board

Technical Field

The invention relates to the technical field of flexible electronic circuit device manufacturing, in particular to chemical copper plating photocuring activation ink and a preparation method thereof, and a preparation method of an addition circuit board.

Technical Field

Currently, there are three main methods for manufacturing Printed Circuit Board (PCB) circuits: subtractive, semi-additive and full-additive. The subtractive method, i.e., the etching method, is the most mature and large-scale printing technology at home and abroad at present. Specifically, the production process is a production process for forming an anti-corrosion layer on a copper plate on a copper-clad plate substrate in a photochemical imaging method, screen printing pattern transfer or electroplating pattern mode, and then corroding the copper foil of a non-pattern part by using an etching solution to form a required circuit.

The additive process is a process of selectively depositing a conductive metal on the surface of an insulating substrate without a copper clad laminate to form a predetermined wiring pattern, and the wiring pattern is subsequently applied to a printed board, and is called an additive process. The processes can be divided into a semi-additive method, a full-additive method, an LDS method, a direct printing method (printing ink or slurry method) and the like. Compared with the subtractive method, the method has the main advantages that: (1) the production cost is low. In the etching method, most of the non-patterned copper surface in the copper foil is etched by using a common etching solution to be wasted, so that high cost is caused, and the copper foil is not required to be etched by the addition method, so that the cost is saved. (2) The environmental pollution is small. The traditional subtractive process requires a large amount of etching solution, generates a plurality of byproducts containing heavy metal ions, the discharge of the etching solution seriously pollutes the environment, and the electroplating process in the additive process also pollutes the environment, but the degree of the electroplating process is far lower than that of the subtractive process. (3) The production process is simple. The addition method reduces the etching process and improves the production efficiency. (4) High precision. The subtractive method is affected by factors such as etching, and it is difficult to fabricate a fine line having a line width/line pitch of less than 50 μm. In the addition method, the hole wall and the lead are simultaneously plated with copper chemically, so that the copper layer is ensured to be uniform and consistent in thickness, and the requirement of the printed board with high thickness-diameter ratio is met.

The direct printing method is to directly print patterns on a flexible insulating substrate by using functional ink or slurry to obtain required circuits. The method is mainly applied to the specific fields of manufacturing RFID electronic tag antennas and the like. The main advantages are 1) simple process and high efficiency. The required pattern can be directly printed on the substrate by a microelectronic printer and other equipment; 2) the cost is low. The raw material cost required in the direct printing method is low and the waste of the raw material is less; 3) is green and environment-friendly. The activated ink adopted by the direct printing method can be directly printed on a substrate, does not contain corrosive chemical reagents, and is green and environment-friendly.

However, most of the inks use metal ions as catalysts in the inks based on the stability of the printing inks and the curing manner and time of the inks, so that on one hand, inorganic metal ions are not easily dispersed in organic resins, and on the other hand, even if the metal ions of the catalysts are dissolved in advance by using a metal ion aqueous solution and then added into the organic resins, the effect of uniform mixing cannot be achieved; inks are generally prepared which require thermal curing at high temperatures, which are high and long. In addition, the metal nanoparticles are used as the activator, so that the use amount of the metal particles is large, and the cost is high especially for the noble metal nanoparticles.

Accordingly, the prior art is yet to be improved and developed.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide the chemical copper plating photo-curing activation ink, the preparation method thereof and the preparation method of the flexible circuit board, and aims to solve the problems of poor stability, high curing temperature and long time of the existing printing ink.

The technical scheme of the invention is as follows:

the chemical copper plating photo-curing activation ink comprises an organic solvent, a carbon-supported metal nano composite material, a prepolymer monomer, an active diluent monomer, a photoinitiator and an auxiliary agent, wherein the carbon-supported metal nano composite material is dissolved in the organic solvent and consists of carbon black and a metal nanoparticle catalyst.

The chemical copper plating photo-curing activation ink comprises, by mass, 32-68% of a prepolymer monomer, 20-40% of an active diluent monomer, 4-7% of a photoinitiator, 1-2% of an auxiliary agent, 5-15% of carbon black and 10-30% of a metal nanoparticle catalyst.

The chemical copper plating photo-curing activation ink is characterized in that the metal nanoparticle catalyst is one or two of nano silver and nano copper; and/or the prepolymer monomer is one or more of epoxy acrylic resin, polyester acrylate and polyurethane acrylate.

The chemical copper plating photo-curing activation ink is characterized in that the active diluent monomer is one or more of methacrylic acid-beta-hydroxyethyl ester, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate.

The chemical copper plating photo-curing activation ink is characterized in that the photoinitiator is one or more of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propane, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate, 2-isopropyl thioxanthone and ethyl p-N, N-dimethylaminobenzoate.

The chemical copper plating photo-curing activation ink comprises an auxiliary agent, a coupling agent, a defoaming agent, a dispersing agent and one or more leveling agents.

A preparation method of electroless copper plating photo-curing activation ink comprises the following steps:

mixing a metal compound solution and carbon black, adding a reducing agent, reducing the metal compound into metal nanoparticles under the water bath heating condition, and carrying the metal nanoparticles on the carbon black to prepare a carbon-supported metal nano composite material;

and mixing the carbon-supported metal nano composite material with a prepolymer monomer, an active diluent monomer and a photoinitiator to prepare the chemical copper plating photo-curing activated ink.

A method for preparing an addition circuit board comprises the following steps:

filling the chemical copper plating photocuring activation ink into a printer, printing a preset circuit diagram on an insulating base material, and performing photocuring treatment to obtain a patterned substrate;

and putting the patterned substrate into a pre-prepared copper plating solution, and performing chemical copper deposition to obtain the circuit board.

The preparation method of the addition circuit board comprises the steps that the copper plating solution comprises sodium hydroxide, sodium potassium tartrate tetrahydrate, copper sulfate pentahydrate, disodium ethylene diamine tetraacetic acid dihydrate, potassium ferrocyanide and formaldehyde.

The preparation method of the addition circuit board comprises the following steps of printing a preset circuit diagram on a flexible insulating base material and carrying out photocuring treatment, wherein the steps of pretreating the flexible insulating base material comprise:

cleaning the insulating base material to obtain a cleaned insulating base material;

putting the cleaned insulating base material into alkaline degreasing liquid, and performing degreasing treatment at 50-80 ℃ to obtain a degreased insulating base material, wherein the alkaline degreasing liquid consists of sodium hydroxide, sodium dodecyl benzene sulfonate, sodium carbonate and sodium phosphate dodecahydrate;

and (3) putting the deoiled insulating base material into a modified adsorption liquid heated to 50 ℃ for modification treatment to obtain a modified flexible insulating base material, wherein the modified adsorption liquid consists of 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, methanol, isopropanol, acetylacetone, deionized water and ethylene glycol monomethyl ether.

Has the advantages that: the invention provides chemical copper plating photo-curing activation ink and a preparation method thereof, and a preparation method of an addition circuit board, wherein a low-cost carbon-supported metal nano composite material is adopted to replace noble metal palladium as a catalyst, so that the production cost is reduced, and excellent stability and catalytic performance are endowed to the chemical copper plating photo-curing activation ink, the chemical copper plating photo-curing activation ink is uniform and stable slurry, and the chemical copper plating photo-curing activation ink can be sealed and stored at room temperature for one month and still keeps the original state; the chemical copper plating photo-curing activation ink can achieve the effect of complete curing within a few seconds under the condition of ultraviolet illumination, and the production efficiency is greatly improved; the chemical copper plating photo-curing activation ink can also be directly in selective patterning design on a base material, gives flexibility to a circuit, and meets the development of the Printed Circuit Board (PCB) industry to the field of addition circuit boards.

Drawings

FIG. 1 is a flow chart of a method for preparing the photo-curing activated ink for electroless copper plating.

Fig. 2 is a flow chart of a manufacturing method of an additive circuit board.

FIG. 3 is a graph of EDS spectroscopy analysis of the composition of a copper layer and its crystallization after electroless copper plating in a photocured patterned circuit.

Fig. 4 is an XRD chart when the composition of a copper layer and its crystallization are analyzed after electroless copper plating in a photo-cured patterned circuit.

FIG. 5 is a graph showing the results of electron microscope observation of the conductive wiring after electroless copper plating.

FIG. 6 is a graph showing the results of a bendability test performed on the conductive traces after electroless copper plating.

FIG. 7 is a graph of the results of a test conducted on copper electroless plated conductive traces to connect LED lights.

Detailed Description

The invention provides chemical copper plating photocuring activation ink, a preparation method thereof and a preparation method of an addition circuit board, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The invention provides chemical copper plating photocuring activation ink which comprises an organic solvent, a carbon-supported metal nano composite material, a prepolymer monomer, an active diluent monomer, a photoinitiator and an auxiliary agent, wherein the carbon-supported metal nano composite material is dissolved in the organic solvent and consists of carbon black and a metal nanoparticle catalyst.

According to the invention, the low-cost carbon-supported metal nano composite material is adopted to replace noble metal palladium as a catalyst, so that the production cost is reduced, and the chemical copper plating photo-curing activated ink is endowed with excellent stability and catalytic performance, is uniform and stable slurry, and can be preserved in a sealed manner for one month at room temperature and still keep the original shape; the chemical copper plating photo-curing activation ink can achieve the effect of complete curing within a few seconds under the condition of ultraviolet illumination, and the production efficiency is greatly improved; the chemical copper plating photo-curing activation ink can also be directly in selective patterning design on a flexible substrate, gives flexibility to a circuit, and meets the development of the Printed Circuit Board (PCB) industry to the field of addition circuit boards.

In the invention, the reactive diluent monomer is a small molecule with certain functionality and participates in a curing reaction, so that the viscosity and the curing speed of the ink can be adjusted. By way of example, the present invention requires that the reactive diluent monomer used has a functionality of 2 to 4, and is one or more of, but not limited to, beta-hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate.

In the invention, after absorbing UV light energy, the photoinitiator can generate free radicals to initiate the ink to generate polymerization reaction, specifically, unsaturated bonds contained in the prepolymer monomer can generate chain reaction during UVLED photocuring, linear resin is converted into a network structure, and the prepolymer monomer in the invention is the skeleton of the whole ink system. The present invention requires that the photoinitiator used is a mixed system of radical polymerization and cation-initiated polymerization, and the photoinitiator is one or more of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propane, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate, 2-isopropyl thioxanthone and ethyl p-N, N-dimethylaminobenzoate, but is not limited thereto; the prepolymer monomer is one or more of epoxy acrylic resin, polyester acrylate and polyurethane acrylate, but is not limited thereto.

In the invention, the auxiliary agent comprises one or more of a coupling agent, a defoaming agent, a dispersing agent and a leveling agent, wherein the coupling agent can connect organic resin and inorganic nanoparticles, the defoaming agent can eliminate bubbles mixed in the ink in the stirring process, the dispersing agent enables a filler in the ink to be better compatible with main resin and not easy to delaminate and precipitate, and the leveling agent can enable the ink to be smoothly coated on the surface of a substrate of a printing stock.

In the invention, the carbon-supported metal nano composite material consists of carbon black and a metal nano particle catalyst, and the carbon black serving as a filler can adsorb the metal nano particle catalyst, so that the wear resistance of the ink layer is improved, and better stability and catalytic performance are endowed. By way of example, the metal nanoparticle catalyst is one or two of nano silver and nano copper, but is not limited thereto.

In some embodiments, in the electroless copper plating photo-curing activation ink, the mass percentage of the prepolymer monomer is 32-68%, the mass percentage of the reactive diluent monomer is 20-40%, the mass percentage of the photoinitiator is 4-7%, the mass percentage of the auxiliary agent is 1-2%, the mass percentage of the carbon black is 5-15%, and the mass percentage of the metal nanoparticle catalyst is 10-30%.

In some embodiments, there is also provided a method for preparing an electroless copper plating photo-curing activation ink, as shown in fig. 1, comprising the steps of:

s10, mixing the metal compound solution and carbon black, adding a reducing agent, reducing the metal compound into metal nano particles under the water bath heating condition, and loading the metal nano particles on the carbon black to prepare the carbon-supported metal nano composite material;

s20, mixing the carbon-supported metal nano composite material with a prepolymer monomer, an active diluent monomer and a photoinitiator to prepare the chemical copper plating photo-curing activated ink.

In this embodiment, when preparing the chemical copper plating photo-curing activation ink, the carbon-supported metal nanocomposite, the prepolymer monomer, the reactive diluent monomer and the photoinitiator need to be effectively and fully stirred to be uniformly dispersed. The chemical copper plating photo-curing activation ink prepared by the embodiment is uniform and stable slurry, and can be sealed and stored at room temperature for one month and still keep the original shape; the chemical copper plating photo-curing activation ink can achieve the effect of complete curing within a few seconds under the condition of ultraviolet illumination, and the production efficiency is greatly improved; the chemical copper plating photo-curing activation ink can also be directly in selective patterning design on a base material, gives flexibility to a circuit, and meets the development of the Printed Circuit Board (PCB) industry to the field of addition circuit boards.

In some embodiments, there is also provided a method for manufacturing a flexible wiring board, as shown in fig. 2, which includes the steps of:

s100, filling the chemical copper plating photo-curing activation ink into a printer, printing a preset circuit diagram on a flexible insulating base material, and carrying out photo-curing treatment to obtain a patterned substrate;

s200, placing the patterned substrate into a pre-prepared copper plating solution, and performing chemical copper deposition to obtain the flexible circuit board.

In this example, the copper plating solution includes sodium hydroxide, sodium potassium tartrate tetrahydrate, copper sulfate pentahydrate, disodium ethylenediaminetetraacetic acid dihydrate, potassium ferrocyanide, and formaldehyde. The chemical copper plating photo-curing activation ink has the advantages of being strong in stability, capable of being cured by ultraviolet light and short in curing time, so that the chemical copper plating photo-curing activation ink can be directly designed in a selective pattern on a base material, flexibility is given to a circuit, and the development of the Printed Circuit Board (PCB) industry to the field of addition circuit boards is met.

In some embodiments, before printing the predetermined pattern on the insulating substrate and performing the photo-curing process, the method further includes a step of pre-treating the insulating substrate, which includes: cleaning the insulating base material to obtain a cleaned insulating base material; putting the cleaned insulating base material into alkaline degreasing liquid, and performing degreasing treatment at 50-80 ℃ to obtain a degreased insulating base material, wherein the alkaline degreasing liquid consists of sodium hydroxide, sodium dodecyl benzene sulfonate, sodium carbonate and sodium phosphate dodecahydrate; and (3) putting the deoiled insulating base material into a modified adsorption solution heated to 50 ℃ for modification treatment to obtain the modified insulating base material, wherein the modified adsorption solution consists of 3-aminopropyl triethoxysilane, 3-mercaptopropyl triethoxysilane, methanol, isopropanol, acetylacetone, deionized water and ethylene glycol monomethyl ether.

The invention is further illustrated by the following specific examples:

example 1

Preparing the carbon-supported silver nanoparticle catalyst by a liquid-phase chemical reduction method:

1) weighing 1.7g of silver nitrate, dissolving the silver nitrate in 100ml of ethylene glycol, marking as solution A, and fully stirring;

2) weighing 3.15g of PVP, dissolving in 100ml of ethylene glycol, uniformly dispersing, adding into the solution A, and fully stirring the mixed solution to obtain solution B;

3) weighing 5g of carbon black, dissolving the carbon black in the mixed solution B, and fully and uniformly stirring to obtain mixed solution C;

4) weighing 1g of NaBH₄Dissolving in 200ml of ethylene glycol, adding the mixture into a separating funnel, controlling the dropping speed, and adding a reducing agent NaBH at the dropping speed of 1 drop/s as much as possible₄Adding the mixture into the mixed solution C, and reacting for 1h in water bath at 50 ℃ when the reducing agent is added.

5) And centrifuging the reacted solution by using absolute ethyl alcohol at the rotating speed of 12000r/min for three times, wherein each time is 5min, and then putting the centrifuged sample into a vacuum drying oven to be dried for later use to prepare the carbon-supported silver nanoparticle catalyst.

Example 2

Preparation of activated ink:

mixing prepolymer resins (PUA and PEA), reactive diluent monomers (TPGDA and TMPTA), photoinitiators (ITX, 907 and EDB) and auxiliaries (coupling agent, defoaming agent, dispersing agent and leveling agent) according to the proportion shown in Table 1, and fully and uniformly stirring to obtain a mixed solution;

and adding the pre-ground and weighed Ag/C composite powder into the mixed solution, uniformly stirring and dispersing the mixture, and stirring the mixture at a high rotating speed for 12 hours to obtain the activated ink.

TABLE 1 activated ink formulation (total 10g)

Example 3

Before printing ink by micro-electronics, a substrate needs to be pretreated, the substrate is a Polyimide film (PI, Polyimide), a Polyethylene terephthalate film (PET) or a paper-based film, taking PET as an example, and the method comprises the following specific steps:

step 1: cleaning of

Cutting the flexible PET substrate into a shape of 5cm multiplied by 7cm, sequentially soaking the flexible PET substrate in deionized water and absolute ethyl alcohol, and ultrasonically cleaning for 15-20 min in an ultrasonic machine;

step 2: oil removal

1) And preparing an alkaline degreasing fluid (the degreasing fluid formula is shown in table 2), heating the degreasing fluid to 50-80 ℃ in a water bath, and then soaking the flexible PET substrate cleaned in the previous step in the degreasing fluid for treatment for 0.5-1 h.

TABLE 2 alkaline degreasing fluid formula

Name of reagent	Dosage (g/L)
		Sodium hydroxide (NaOH)	20
Sodium Dodecyl Benzene Sulfonate (SDBS)	1
		Sodium carbonate (Na)₂CO₃)	3
Sodium phosphate dodecahydrate (Na)₃PO₄·12H₂O)	5

2) And then using deionized water to wash the flexible PET substrate, putting the PET substrate into the deionized water and absolute ethyl alcohol in sequence, ultrasonically cleaning for 60s, and completely drying for later use.

3) Surface self-assembly modification treatment (formula of modified adsorption solution is shown in tables 3 and 4)

Heating the modified adsorption solution to 50 ℃ by using a water bath kettle, after the temperature is stable, adding a cleaned and dried PET base material, and carrying out self-assembly reaction in the modified adsorption solution for 15-30 min;

after the reaction is finished, naturally drying the PET substrate, and ultrasonically cleaning the self-assembled modified PET substrate for 30-60 s by using isopropanol and deionized water respectively when the substrate is basically dried;

and after cleaning, putting the modified PET substrate into a vacuum drying oven, and heating and drying at the temperature of 70 ℃ for 0.5-1 h to finish the self-assembly modification process.

TABLE 3 sorbent solute fluid formulation

Name of reagent	Dosage (ml)
		3-Aminopropyltriethoxysilane (APTES)	60
3-Mercaptopropyltriethoxysilane (MPTES)	20
		Methanol (CH)₃OH)	6
Isopropanol (C)₃H₈O)	2
		Acetylacetone (C)₅H₈O₂)	2
Deionized water	10

TABLE 4 adsorbent solvent fluid formulations

Name of reagent	Dosage (ml/L)
		Isopropanol (C)₃H₈O)	600
Ethylene glycol methyl ether (C)₃H₈O₂)	300

Printing patterned lines on a flexible substrate with a microelectronic printer:

and (3) putting the fully stirred ink into an ink tube of a microelectronic printer, and printing a pre-designed pattern on the pretreated flexible base material by testing the dispensing printing pressure and the height between the needle head and the substrate in a dispensing mode. Further, in order to ensure that the printing ink is smoothly printed on the flexible base material, the air pressure in the parameter setting of the microelectronic printer is controlled to be 30-70 kPa, and the distance between the dispensing needle head and the flexible base material is controlled to be 0.05-0.1 mm.

Example 4

Photocuring of patterned lines

Putting the ink layer just printed on the flexible substrate into a UV (ultraviolet) curing machine for curing treatment, wherein the curing time is as follows: 25 s; curing lamp power: 100 percent; distance between the UVLED lamp and the substrate: 3 cm.

Example 5

Electroless copper plating of photocured patterned circuits

Putting the completely cured flexible base material into a prepared copper plating solution, and carrying out chemical copper deposition at a copper plating temperature: water bath at 50 ℃; copper plating time: 0.5 to 1 hour. The formula of the copper plating solution for electroless copper plating is as follows: sodium hydroxide (15g/L), potassium sodium tartrate tetrahydrate (15g/L), copper sulfate pentahydrate (15g/L), disodium ethylenediaminetetraacetate dihydrate (20g/L), potassium ferrocyanide (1g/L), and formaldehyde solution (95 mL/L).

After the copper is electroless plated in the photocuring patterned circuit in the embodiment, the composition and crystallization of the copper layer are analyzed, and as shown in fig. 3 and 4, it can be seen from fig. 3 that the electroless copper plating layer contains Cu element, and other elements may be impurities introduced by the sample stage unclean, but the content is almost negligible. Fig. 4 shows that the copper in the electroless copper plating layer is well crystallized and only diffraction peaks of pure Cu and no miscellaneous peaks of other oxides appear, and that the carbon peaks and Ag peaks appear due to the carbon-supported silver nanoparticles in the ink.

The conductive circuit after electroless copper plating of this embodiment is subjected to electron microscope observation, and the result is shown in fig. 5, it can be seen from fig. 5 that the surface of the conductive circuit after electroless copper plating is smooth and complete, and it can be seen that copper particles on the surface are closely arranged, and there are no obvious loose holes, which is also one of the reasons why the copper circuit can conduct electricity normally.

The results of the bending test on the conductive circuit after electroless copper plating in this embodiment are shown in fig. 6, and it can be seen from fig. 6 that the copper circuit of the flexible copper circuit is still in a good and unbroken state no matter the flexible copper circuit is bent inward or outward at a large angle, which indicates that the flexible copper circuit meets the development requirements of the flexible electronic circuit.

The test results of the copper-plated conductive circuit connection LED lamps of this embodiment are shown in fig. 7, and it can be seen from fig. 7 that the LED lamps can work normally regardless of whether the flexible copper circuit is straight, inward or outward.

In summary, the invention adopts a liquid phase chemical reduction method to reduce the metal compound into metal nanoparticles, and adds carbon black to prepare a composite material of carbon-supported metal nanoparticles, then mixes the carbon-supported metal nanoparticles with a prepolymer monomer, an active diluent monomer, a photoinitiator and an auxiliary agent to prepare chemical copper plating photocuring activation ink, then loads the ink into a microelectronic printer, and prints out a preset circuit diagram on a pretreated flexible insulating substrate; and then the substrate coated with the pattern is subjected to photocuring and placed in copper plating solution for electroless copper plating, and once the electroless copper plating is initiated, the deposited copper layer can be further subjected to autocatalytic copper plating due to the fact that the functional printing ink contains a nano particle catalyst for catalyzing the electroless copper plating, and finally the metallization of the pattern can be realized.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims

1. The chemical copper plating photocuring activation ink is characterized by comprising an organic solvent, a carbon-supported metal nano composite material, a prepolymer monomer, an active diluent monomer, a photoinitiator and an auxiliary agent, wherein the carbon-supported metal nano composite material is dissolved in the organic solvent and consists of carbon black and a metal nanoparticle catalyst.

2. The electroless copper plating photocuring activation ink as recited in claim 1, wherein in the electroless copper plating photocuring activation ink, the mass percentage of a prepolymer monomer is 32-68%, the mass percentage of a reactive diluent monomer is 20-40%, the mass percentage of a photoinitiator is 4-7%, the mass percentage of an auxiliary agent is 1-2%, the mass percentage of carbon black is 5-15%, and the mass percentage of a metal nanoparticle catalyst is 10-30%.

3. The electroless copper plating photocuring activation ink as recited in any one of claims 1 to 2, wherein the metal nanoparticle catalyst is one or both of nano silver and nano copper; and/or the prepolymer monomer is one or more of epoxy acrylic resin, polyester acrylate and polyurethane acrylate.

4. The electroless copper plating photo-curing activation ink as claimed in any one of claims 1-2, wherein the reactive diluent monomer is one or more of beta-hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate.

5. The electroless copper plating photocuring activation ink as defined in any one of claims 1 to 2, wherein the photoinitiator is one or more of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propane, 1-hydroxycyclohexyl phenyl ketone, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-isopropyl thioxanthone and ethyl p-N, N-dimethylaminobenzoate.

6. The electroless copper plating photocuring-activated ink as recited in claim 3, wherein the auxiliary agent comprises one or more of a coupling agent, a defoaming agent, a dispersing agent and a leveling agent.

7. A method for preparing the photo-curing activating ink for electroless copper plating according to any one of claims 1 to 6, which comprises the steps of:

8. A method for manufacturing an addition circuit board is characterized by comprising the following steps:

filling the electroless copper plating photocuring activation ink as defined in any one of claims 1 to 6 into a printer, printing a preset circuit diagram on an insulating substrate and carrying out photocuring treatment to obtain a patterned substrate;

and putting the patterned substrate into a pre-prepared copper plating solution, and carrying out chemical copper deposition to obtain the addition circuit board.

9. The method of manufacturing an addition wiring board according to claim 8, wherein the copper plating solution includes sodium hydroxide, potassium sodium tartrate tetrahydrate, copper sulfate pentahydrate, disodium ethylenediaminetetraacetic acid dihydrate, potassium ferrocyanide, and formaldehyde.

10. The method for producing an addition-type wiring board according to claim 8, further comprising a step of pretreating the insulating substrate before printing a predetermined wiring pattern on the insulating substrate and performing a photocuring treatment, the step comprising:

and (3) putting the deoiled insulating base material into a modified adsorption solution heated to 50 ℃ for modification treatment to obtain the modified insulating base material, wherein the modified adsorption solution consists of 3-aminopropyl triethoxysilane, 3-mercaptopropyl triethoxysilane, methanol, isopropanol, acetylacetone, deionized water and ethylene glycol monomethyl ether.