CN104789949B - The collocation method of self-catalysis electroless copper epoxy resin solution and electroless copper plating method - Google Patents
The collocation method of self-catalysis electroless copper epoxy resin solution and electroless copper plating method Download PDFInfo
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Abstract
The collocation method of self-catalysis electroless copper epoxy resin solution and electroless copper plating method, belong to technical field of material surface treatment.Comprise the following steps：Active ion source is added in organic solvent in the case of being stirred continuously, and after adding a certain amount of curing catalysts, is sufficiently stirred for, form uniform activator solution；Then while stirring epoxy resin is added to by a certain percentage formation epoxy resin organic solution in firming agent；While being stirred continuously, activator solution is slowly added in epoxy resin organic solution and forms uniform and stable system, that is, obtain the epoxy resin solution with autocatalytic activity electroless copper.The resin solution having configured the tape casting or silk screen print method are formed uniform coating in printed circuit board substrate, again through operations such as solidification, microetch, reduction, chemical platings, can get the plating piece of glitter powder redness copper coating, through the layers of copper resin-bonded power of performance test sample, electrical conductivity splendid it is adaptable to chemical-copper-plating process.
Description
Technical field
The invention belongs to technical field of material surface treatment, it is related to a kind of configuration of printed circuit board electroless copper activator
Method and the method carrying out electroless copper using it, especially relating to one kind, to have self-catalysis electroless copper reactive epoxies molten
The collocation method of liquid and the method carrying out electroless copper using it.
Background technology
Mainly addition is realized using chemical plating and electroplating technology in printed circuit board (PCB) conducting wire manufacturing process
Normal road makes and hole metallization.Its principle be first pass through electroless copper in the micropore of PCB substrate or surface deposit one layer
Thin copper, is allowed to conductive capability, then utilizes electroplating technology to thicken, and obtains target electronic circuit or the metal realizing via
Change.
The most widely used PCB substrate material is epoxy resin at present.Chemical-copper-plating process flow process generally includes surface
Roughening, sensitization, activation, four steps of electroless copper.Surface coarsening step generally comprises mechanical coarsening and chemical roughening, using relatively
For being widely chemistry roughening, its target is an up binding force of cladding material.In the industrial production, used in chemistry roughening, chemistry is thick
Changing liquid is chromic acid-sulfuric acid or alkalinity potassium permanganate system.However, the waste water that this chemical roughening process is discharged has high pollution
Property, serious harm health.Therefore, PCB Hole Metallization technique introduces black holes technology.Black holes technology will
Fine graphite or charcoal blacking (blank hole liquid) dip-coating form conductive layer, so by surface adsorption on hole wall on epoxy resin
After carry out Direct Electroplating thicken obtain high-quality conductive layer.Wherein, blank hole liquid is generally the organic emulsion containing precious metal ion.
However, this technology can be only applied to printed circuit plate hole technology, but cannot be applied to addition process and make printed circuit board process.Cause
This, goal in research is turned to the printed circuit board baseplate material with electroless copper autocatalytic activity by people.At present, its research side
To as follows：1. access carboxyl, amino, sulfydryl etc. in the structure of macromolecular material using crosslinking technology, active in absorption
Copper, palladium ion, formed implement electroless copper active center.Then, on resin structure, grafting functional group can change base
The electric property (as insulating properties, dielectric constant etc.) of panel material, the mechanical performance of impact material, processing characteristics, affect multi-layer sheet
Inter-layer bonding force, cost etc. of lifting material, directly affect performance and the competitiveness of printed board.And in high density, multilamellar
In printed circuit board processing technology, its application is subject to certain restrictions.2. exploitation has the coating material of catalysis activity, however,
The method has that coating adhesion is poor, and substrate electric property changes, resin film non-chemical plating copper catalysis activity or ion migration
Shortcoming.Therefore, need a kind of new self-catalysis electroless copper epoxy resin solution badly and solve above-mentioned technical problem.
Content of the invention
The technical problem to be solved is to provide a kind of self-catalysis that can be used for Manufacturing Technology for PCB to live
The collocation method of property electroless copper epoxy resin solution and the method carrying out electroless copper using this solution, this solution can be effective
Solve the problems, such as that between active layer and original substrate, adhesion is poor, monoblock substrate can be prevented effectively from using doping reactive resin simultaneously
The technical problems such as the cost that brings, the change of substrate electric property, ion migration.
The technical solution adopted for the present invention to solve the technical problems is：The joining of self-catalysis electroless copper epoxy resin solution
Put method, comprise the following steps：
A. every 0.1～0.5g active ion source is added in 10～20mL organic solvent in the case of being stirred continuously,
And after adding a certain amount of curing catalysts, be sufficiently stirred for, formed uniform activator solution, described curing catalysts with organic
The volume ratio of solvent is 1:15～1:30；
B. while being stirred continuously, epoxy resin is added in firming agent by a certain percentage, forming epoxy resin has
Machine solution, described epoxy resin is 1 with the volume ratio of firming agent:0.75～1:1.2；
C. the activator solution that step A obtains is slowly added into the ring be obtained in step B in the case of being stirred continuously
In oxygen tree fat organic solution, described activator solution is 0.3 with the volume ratio of epoxy resin organic solution:1～1.5:1, formed
Uniform and stable system, that is, obtain the epoxy resin solution with autocatalytic activity electroless copper.
Specifically, the active ion source in described step A includes dissolving in acylate in organic solvent, metal-carbonyl
One or more of compound, metal alkoxide, acetyl acetone complex, described active ion source include acid chloride, oxalic acid palladium,
Silver benzoate, silver acetate, silver oxalate, silver acetate, Tubercuprose., copper acetate, cupric oxalate, carbonyl copper, carbonyl silver, cupric alkoxide, silver-colored alcohol
One or more of salt, acetylacetone copper or acetylacetone,2,4-pentanedione silver.
Specifically, the organic solvent in described step A is acetone, butanone, hexamethylene, ethylene glycol, Polyethylene Glycol, isopropyl
One or more of alcohol, oxolane, acetylacetone,2,4-pentanedione.
Further, described step A also includes for dispersant and/or diluent being added to obtained activator solution
In, it is sufficiently stirred for, forms final activator solution, described dispersant is ethylenediamine, dimethylformamide, dimethylacetamide
One or more of amine, triethylamine.
Specifically, described curing catalysts are tetraethylammonium bromide, dimethyl benzylamine, 2-ethyl-4-methylimidazole, 1- cyanogen
One of ethyl -2-ethyl-4-methylimidazole, 2,4,6- tri- (dimethylaminomethyl) phenol, organic phosphine/bromo-complex or
Multiple；Described firming agent is methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, hexahydro
One or more of phthalate anhydride, triethylene tetramine, diethylaminopropylamine, m-diaminobenzene..
Preferably, the epoxy resin in described step B is glycidyl ether type epoxy resin, (+)-2,3-Epoxy-1-propanol esters asphalt mixtures modified by epoxy resin
One or more of fat, glycidyl amine epoxy resin, linear aliphatic epoxy resin or alicyclic based epoxy resin.
Further, the epoxy resin temperature in described step B is 40～60 DEG C, adds it to the speed in firming agent
Scope is 2～5mL/min.
Using the self-catalysis electroless copper epoxy resin solution method that carries out electroless copper of above-mentioned steps configuration, including with
Lower step：
A. toasted, by joining of above-mentioned self-catalysis electroless copper epoxy resin solution after the substrate of cleaning printed circuit board
The self-catalysis electroless copper epoxy resin solution that method of putting is obtained is coated uniformly on substrate, and is placed on solidification one in baking oven
Fix time；
B. take out rapidly in the substrate immersion micro-corrosion liquid after solidification step A being obtained, be placed in reducing solution, soak
Take out after certain time, and deionized water is cleaned；
C. substrate is placed in chemical bronze plating liquid, takes out after chemical plating 20～45min at a temperature of 30～45 DEG C, spend
Ionized water is cleaned and is dried.
Specifically, the micro-corrosion liquid in described step B be acetone, butanone, hexamethylene, ethylene glycol, Polyethylene Glycol, isopropanol,
In oxolane, acetylacetone,2,4-pentanedione, chloroform or ethyl acetate；Described reducing solution be sodium borohydride, hydrazine hydrate, formaldehyde,
Ascorbic acid, sodium hydride, sodium thiosulfate.
Specifically, the electroless copper formula of liquid in described step C is：Sodium hydroxide, 8g；Copper sulphate pentahydrate, 8g；Tartaric acid
Potassium sodium, 8g；Edetate disodium, 8g；Polyethylene glycol 6000,25mg；Potassium iodide, 5mg；Concentration is 37% formaldehyde, 6～
8cm3；Water, 500cm3.
The invention has the beneficial effects as follows：The self-catalysis electroless copper epoxy resin solution of present invention configuration, enables low
The lower self-catalysis electroless copper of temperature, its copper-plating technique is similar to existing chemical-copper-plating process, and therefore enterprise need not set to existing process
For being transformed on a large scale and can apply, greatly save cost；This solution homogeneous transparent, stable type is good, is suitable to protect for a long time
Deposit；Because the main component of this solution is consistent with epoxide resin type PCB substrate, therefore can produce well with substrate after hardening
Combination, even if being not easy to peel off in high temperature or wet environment, warpage, the electric property of substrate will not be changed；In base
Plate surface forms metal ion in film type active layer and can enter in coating by method of reducing, it is possible to decrease ion migration phenomenon pair
The impact in printed circuit board life-span, extends device service life.Plating piece surface layers of copper using its electroless copper is evenly distributed, and puts down
Whole degree is high, and quality is good.The present invention is applied to chemical-copper-plating process.
Brief description
Fig. 1 is the configuration flow figure of the self-catalysis electroless copper epoxy resin solution of the present invention；
Fig. 2 is the preparation flow figure carrying out electroless copper in the present invention using self-catalysis electroless copper epoxy resin solution；
Fig. 3 is using layers of copper metallurgical microscope picture in plating piece surface after method of the present invention chemical plating.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment, describe technical scheme in detail.
As shown in figure 1, the invention provides a kind of collocation method of new self-catalysis electroless copper epoxy resin solution, that is,
Active ion source is added in organic solvent in the case of being stirred continuously, and after adding a certain amount of curing catalysts, fills
Divide stirring, form uniform activator solution；Then while stirring epoxy resin is added to by a certain percentage shape in firming agent
Become epoxy resin organic solution；Finally while being stirred continuously, activator solution is required according to a certain percentage be slowly added to
Form uniform and stable system in epoxy resin organic solution, that is, obtain the epoxy resin with autocatalytic activity electroless copper
Solution.
Embodiment 1
The collocation method of the self-catalysis electroless copper epoxy resin solution of this example comprises the following steps：
1. configure novel active agent solution.
(1) weigh 0.1～0.5g active ion source, stirring, while this active ion source is added to fill 10～
In the beaker of 20mL organic solvent, it is sufficiently stirred for, form uniform activator solution；
Described active ion source can form the slaine of catalytic chemistry copper facing particle, active ion source after referring to be reduced
Including one of the acylate dissolving in organic solvent, metal carbonyl, metal alkoxide, acetyl acetone complex
Or multiple, active ion source specifically include acid chloride, oxalic acid palladium, silver benzoate, silver acetate, silver oxalate, Tubercuprose., copper acetate,
One or more of cupric oxalate, carbonyl copper, carbonyl silver, cupric alkoxide, silver-colored alkoxide, acetylacetone copper or acetylacetone,2,4-pentanedione silver.Organic
Solvent is one of acetone, butanone, hexamethylene, ethylene glycol, Polyethylene Glycol, isopropanol, oxolane, acetylacetone,2,4-pentanedione or many
Kind.
Carrying out configuring in activator solution, finally comprising 0.1～0.5g active ion in every 10～20mL organic solvent
Source.
(2) dispersant and diluent are added.Dispersant and diluent are added to the activator solution be obtained in step (1)
In, it is sufficiently stirred for；
The required composition of the technical program be epoxy resin, firming agent, curing catalysts, composition be acylate activity
Ion source and organic solvent, can adding ingredient be dispersant and diluent.Dispersant is from dissolvable epoxy resin and its solidification
The organic ligand of agent low boiling organic amine, specifically, can be selected for ethylenediamine, dimethylformamide, dimethyl acetylamide, three second
One or more of amine.Add organic ligand, play regulation Resin Flow and viscosity, and lifting acylate isoreactivity
Ion source dissolubility in organic solvent, is added without also enabling the technique effect of the technical program.
(3) while stirring, curing catalysts are slowly dropped in the solution that step (2) obtains, you can obtain new
Activator solution.
Curing catalysts are tetraethylammonium bromide, dimethyl benzylamine, 2-ethyl-4-methylimidazole, 1- cyanoethyl -2- second
One or more of base -4-methylimidazole, 2,4,6- tri- (dimethylaminomethyl) phenol, organic phosphine/bromo-complex.Organic
Phosphine/bromo-complex is model AO-4：A kind of material of HycatTM.Curing catalysts can add in arbitrary steps, will not
Impact solidification effect.The amount of the curing catalysts needing seldom, but must be added to, and does not use curing catalysts, epoxy resin is no
Method is solidified.The addition of curing catalysts less it is only necessary to epoxy resin volume 1/20 about, or urged from solidification
Agent is 1 with the volume ratio of organic solvent:15～1:30 also may be used.
2. weigh appropriate epoxy resin, firming agent according to recipe requirements, described epoxy resin with the volume ratio of firming agent is
1:0.75～1:1.2, stirring, while epoxy resin is slowly added in firming agent, in order to prevent solution viscosity excessive,
Control temperature when adding epoxy resin at 40～60 DEG C, and control it to be added to the speed in firming agent for 2～5mL/min.
Firming agent is methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, hexahydrobenzene
One or more of dicarboxylic acid anhydride, triethylene tetramine, diethylaminopropylamine, m-diaminobenzene..Anhydrides material may be combined in
Together, amine substance may be mixed together.
Epoxy resin is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, (+)-2,3-Epoxy-1-propanol amine epoxy
One or more of resin, linear aliphatic epoxy resin or alicyclic based epoxy resin.
3. the novel active agent solution that step 1 obtains is required to be slowly added dropwise the ring obtaining into step 2 according to a certain percentage
In oxygen tree fat organic solution, described activator solution is 0.3 with the volume ratio of epoxy resin organic solution:1～1.5:1, fully
Stirring, the epoxy resin solution with self-catalysis electroless copper activity being uniformly mixed.
The self-catalysis electroless copper epoxy resin solution of this example is by epoxy resin, firming agent, curing catalysts, organic acid
The material compositions such as salt/metal carbonyl, dispersant and diluent.This solution, with epoxy resin as film former, is had with metal
Machine hydrochlorate and its coordination compound, metal carbonyl etc. are active ion source, with butanone, hexamethylene, oxolane, second two
The organic solvents such as alcohol, Polyethylene Glycol are dispersant, and the firming agent with anhydride or amine Organic substance as epoxy resin is many with aliphatic
The organic amines such as first amine are metal organic acid salt part, curing catalysts.The transparent clarification of resin solution that the method obtains, has
Good stability.
By the self-catalysis having configured electroless copper epoxy resin solution the tape casting or silk screen print method in printed circuit board
Substrate forms uniform coating, then through operations such as solidification, microetch, reduction, chemical platings, you can obtain light pink copper coating
Plating piece, specifically as shown in Figure 2：Toasted, by self-catalysis electroless copper asphalt mixtures modified by epoxy resin liposoluble after the substrate of cleaning printed circuit board
Liquid is coated uniformly on substrate, and is placed on solidification certain time in baking oven, and oven temperature is set as 120～160 DEG C；To consolidate
Take out rapidly in substrate immersion micro-corrosion liquid after change, be placed in reducing solution, take out after soaking certain time, and use deionization
Water is cleaned；Substrate is placed in chemical bronze plating liquid, after chemical plating 20～45min at a temperature of 30～45 DEG C take out, spend from
Sub- water is cleaned and is dried.Finally can get the plating piece of light pink copper coating, through the layers of copper-resin knot of performance test sample
With joint efforts, electrical conductivity is splendid.
Substrate can select FR-4 base material.Specifically, it is cleaned by ultrasonic printed circuit board using dehydrated alcohol, deionized water
Substrate.Micro-corrosion liquid is high to cured epoxy resin dissolubility but the organic solvent poor to ion source dissolubility.Micro-corrosion liquid is third
Ketone, butanone, hexamethylene, ethylene glycol, Polyethylene Glycol, isopropanol, oxolane, acetylacetone,2,4-pentanedione, chloroform or ethyl acetate.Have
Different types of micro-corrosion liquid mixes effect and can be deteriorated a bit, is therefore typically chosen a kind of micro-corrosion liquid.Described reproducibility
Solution can be reasonable for sodium borohydride, hydrazine hydrate, formaldehyde, ascorbic acid, sodium hydride, this several reproducibility of sodium thiosulfate
Solution.
Because film former for printed circuit board baseplate material and is organic solvent system, effectively solving active layer can be obtained
Adhesion difference problem and original substrate between, active body is metal organic acid salt and its coordination compound, metal carbonyl etc.
It is dissolvable in water the compound in organic solvent, the uniformity of active center distribution can be ensured.In addition, in the activity being formed during plating
The heart, is partly embedded in inside active layer resin, and active centre not only can be prevented oxidized, also can lift coating further simultaneously
Adhesion and substrate between.In practical application, this activator need only need the local of plating to form catalysis in plating
Layer, can avoid cost, the change of substrate electric property, ion migration etc. that monoblock substrate brought using doping reactive resin
Technical problem.
Epoxy resin produces good adhesion with tellite after solidification, inlays gold in the epoxy
Genus ion is formed after being reduced has the copper-plated active metal particles of catalytic chemistry, thus realizing the self-catalysis chemical plating of copper.
This epoxy resin solution cannot be only used for printed circuit board mesoporous metal technique, is also suitable for addition process printed-circuit board manufacturing technology
In fine-line processing procedure.
Fig. 3 is plating piece surface layers of copper metallurgical microscope picture after chemical plating, and white portion is layers of copper it can be seen that on plating piece
Copper coating uniformly, layers of copper is combined preferably with matrix.
Embodiment 2
1. weigh 0.1g Tubercuprose., add butanone-ethylene glycol (1 that quality is 3g：1) in system, wherein, butanone-second two
The volume ratio of alcohol is 1:1, it is sufficiently stirred for making its mix homogeneously, and a small amount of ethylenediamine of Deca is as dispersant, Deca epoxy resin
Curing catalysts, and stir.
2. take 1g bisphenol A-type glycidyl ether, add the methylhexahydrophthalic anhydride that quality is 0.8g, mechanical agitation
20min, forms tetraglycidel ether epoxy resin solution.
3. with dropper, Tubercuprose .-butanone/ethylene glycol solution that step 1 obtains slowly is instilled the glycidyl ether under stirring
In epoxy resin solution, continue stirring 30min after dripping off, obtain cupric epoxy resin solution.
4. choose FR-4 substrate as the substrate of printed circuit board, FR-4 substrate is ultrasonic through dehydrated alcohol, deionized water
Cleaning, puts in 100 DEG C of baking ovens and toasts 1 hour, and the cupric epoxy resin solution in step 3 is uniformly coated in compared with unfertile land dry
On dry FR-4 substrate, it is placed on solidification 10min in 120 DEG C of baking ovens.
5., by 10 seconds in the FR-4 substrate immersion butanone after solidification, take out rapidly, be placed in 1mol/L alkalescence sodium borohydride
In solution, take out after soaking 30s, and deionized water is cleaned；Then FR-4 substrate is placed in chemical bronze plating liquid, at 40 DEG C
At a temperature of take out after chemical plating 25min, deionized water is cleaned and is dried.
Wherein electroless copper formula of liquid is：Sodium hydroxide, 8g；Copper sulphate pentahydrate, 8g；Sodium potassium tartrate tetrahydrate, 8g；Diamidogen tetrem
Acid disodium, 8g；Polyethylene glycol 6000,25mg；Potassium iodide, 5mg；Concentration is 37% formaldehyde, 6～8cm3(stirring is lower to be added)；
Water, 500cm3.
With four probe method measuring samples sheet resistance, in 0.01～1.00 Ω .cm, measurement obtains the square electricity of layers of copper to measurement range
Hinder for 0.10 Ω/.
Embodiment 3
1. weigh 0.1g silver acetate, add in the butanone that quality is 3g, be sufficiently stirred for making its mix homogeneously, and Deca is a small amount of
Ethylenediamine is as dispersant, Deca Epoxy cure catalysts, and stirs.
2. take 1g bisphenol A-type glycidyl ether, add the methylhexahydrophthalic anhydride that quality is 0.8g, mechanical agitation
20min, forms tetraglycidel ether epoxy resin solution.
3. with dropper, the solution that step 1 obtains slowly is instilled in the epoxy resin solution that the step 2 under stirring obtains, drip
Continue stirring 30min after complete, obtain argentiferous epoxy resin solution.
4. FR-4 substrate is cleaned by ultrasonic through dehydrated alcohol, deionized water, puts in 100 DEG C of baking ovens and toast 1 hour, and will
Argentiferous epoxy resin solution in step 3 is uniformly coated in compared with unfertile land and is dried on FR-4 substrate, is placed in 130 DEG C of baking ovens solid
Change 10min.
5., by 10 seconds in the FR-4 substrate immersion butanone after solidification, take out rapidly, be placed in 1mol/L alkalescence sodium borohydride
In solution, take out after soaking 30s, and deionized water is cleaned；Then FR-4 substrate is placed in chemical bronze plating liquid, at 40 DEG C
At a temperature of take out after chemical plating 25min, deionized water is cleaned and is dried.
Using four probe method measuring samples sheet resistance, measurement range obtains the square of layers of copper in 0.01～1.00 Ω .cm, measurement
Resistance is 0.18 Ω/.
Embodiment 4
1. weigh 0.1g silver nitrate, add in the butanone that quality is 3g, be sufficiently stirred for making its mix homogeneously, and Deca is a small amount of
1- cyanoethyl -2-ethyl-4-methylimidazole is as the curing catalysts of epoxy resin, and stirs.
2. take 2g POLYBUTADIENE EPOXY RESIN, add the methylhexahydrophthalic anhydride that quality is 1.5g, machinery stirs
Mix 20min, obtain aliphatic epoxy resin solution.
3. with dropper, the solution that step 1 obtains slowly is instilled in the epoxy resin solution in the step 2 under stirring, drip off
Continue stirring afterwards, obtain argentiferous epoxy resin solution.
4. FR-4 substrate is cleaned by ultrasonic through dehydrated alcohol, deionized water, puts in 100 DEG C of baking ovens and toast 1 hour, and will
Argentiferous epoxy resin solution in step 3 is uniformly coated in compared with unfertile land and is dried on FR-4 substrate, is placed in 120 DEG C of baking ovens solid
Change 10min.
5., by 10 seconds in the FR-4 substrate immersion butanone after solidification, take out rapidly, be placed in 1mol/L alkalescence sodium borohydride
In solution, take out after soaking 30s, and deionized water is cleaned；Then FR-4 substrate is placed in chemical bronze plating liquid, at 40 DEG C
At a temperature of take out after chemical plating 25min, deionized water is cleaned and is dried.
Wherein electroless copper formula of liquid is：Sodium hydroxide, 8g；Copper sulphate pentahydrate, 8g；Sodium potassium tartrate tetrahydrate, 8g；Diamidogen tetrem
Acid disodium, 8g；Polyethylene glycol 6000,25mg；Potassium iodide, 5mg；37% formaldehyde, 6～8cm3(stirring is lower to be added)；Water, 500cm3.
Measure the sample sheet resistance of this example formation with four probe method, measurement range obtains copper in 0.01～1.00 Ω .cm, measurement
The square resistance of layer is 0.15 Ω/.
Embodiment 5
1. weigh 0.1g silver nitrate, add in the isopropanol that quality is 3g and 0.1g silane coupler KH-560, silver nitrate
It is inorganic salt, silane coupler KH-560 is to increase inorganic salt particle solubility property in organic solvent, being sufficiently stirred for
Make its mix homogeneously, and a small amount of ethylenediamine of Deca, Deca Epoxy cure catalysts, and stir.
2. take 1g bisphenol A-type glycidyl ether, add the methylhexahydrophthalic anhydride that quality is 0.8g, mechanical agitation
20min, obtains epoxy resin solution.
3. with dropper, the solution that step 1 obtains slowly is instilled in the epoxy resin solution in the step 2 under stirring, drip off
Continue stirring afterwards, obtain argentiferous epoxy resin solution.
4. FR-4 substrate is cleaned by ultrasonic through dehydrated alcohol, deionized water, puts in 100 DEG C of baking ovens and toast 1 hour, and will
Argentiferous epoxy resin solution in step 3 is uniformly coated in compared with unfertile land and is dried on FR-4 substrate, is placed in 120 DEG C of baking ovens solid
Change 10min.
5., by 10 seconds in the FR-4 substrate immersion butanone after solidification, take out rapidly, be placed in 1mol/L alkalescence sodium borohydride
In solution, take out after soaking 30s, and deionized water is cleaned；Then FR-4 substrate is placed in chemical bronze plating liquid, at 40 DEG C
At a temperature of take out after chemical plating 25min, deionized water is cleaned and is dried.
Wherein electroless copper formula of liquid is：Sodium hydroxide, 8g；Copper sulphate pentahydrate, 8g；Sodium potassium tartrate tetrahydrate, 8g；Diamidogen tetrem
Acid disodium, 8g；Polyethylene glycol 6000,25mg；Potassium iodide, 5mg；37% formaldehyde, 6～8cm3(stirring is lower to be added)；Water, 500cm3.
With four probe method measuring samples sheet resistance, in 0.01～1.00 Ω .cm, measurement obtains the square electricity of layers of copper to measurement range
Hinder for 0.20 Ω/.
Embodiment 6
1. weigh 0.2g carbonyl copper, add in the butanone that quality is 3g, be sufficiently stirred for making its mix homogeneously, and Deca is a small amount of
1- cyanoethyl -2-ethyl-4-methylimidazole, and stir.
2. take 1g bisphenol A-type glycidyl ether, add the methylhexahydrophthalic anhydride of quality 0.8g, mechanical agitation
20min, obtains epoxy resin solution.
3. with dropper, the solution that step 1 obtains slowly is instilled in the epoxy resin solution in the step 2 under stirring, drip off
Continue stirring afterwards, obtain cupric epoxy resin solution.
4. FR-4 substrate is cleaned by ultrasonic through dehydrated alcohol, deionized water, puts in 100 DEG C of baking ovens and toast 1 hour, and will
Cupric epoxy resin solution in step 3 is uniformly coated in compared with unfertile land and is dried on FR-4 substrate, is placed in 120 DEG C of baking ovens solid
Change 10min.
5., by 10 seconds in the FR-4 substrate immersion butanone after solidification, take out rapidly, be placed in 1mol/L alkalescence sodium borohydride
In solution, take out after soaking 30s, and deionized water is cleaned；Then FR-4 substrate is placed in chemical bronze plating liquid, at 40 DEG C
At a temperature of take out after chemical plating 25min, deionized water is cleaned and is dried.Wherein electroless copper formula of liquid is：Sodium hydroxide,
8g；Copper sulphate pentahydrate, 8g；Sodium potassium tartrate tetrahydrate, 8g；Edetate disodium, 8g；Polyethylene glycol 6000,25mg；Potassium iodide,
5mg；37% formaldehyde, 6～8cm3(stirring is lower to be added)；Water, 500cm3.
With four probe method measuring samples sheet resistance, in 0.01～1.00 Ω .cm, measurement obtains the square electricity of layers of copper to measurement range
Hinder for 0.22 Ω/.
Claims (10)
1. the collocation method of self-catalysis electroless copper epoxy resin solution is it is characterised in that comprise the following steps：
A. every 0.1～0.5g active ion source is added in 10～20mL organic solvent in the case of being stirred continuously, and plus
After entering a certain amount of curing catalysts, it is sufficiently stirred for, form uniform activator solution, described curing catalysts and organic solvent
Volume ratio be 1:15～1:30；
B. while being stirred continuously, epoxy resin is added in firming agent by a certain percentage, forms epoxy resin organic molten
Liquid, described epoxy resin is 1 with the volume ratio of firming agent:0.75～1:1.2；
C. the activator solution that step A obtains is slowly added into the asphalt mixtures modified by epoxy resin be obtained in step B in the case of being stirred continuously
In fat organic solution, described activator solution is 0.3 with the volume ratio of epoxy resin organic solution:1～1.5:1, formed uniformly
Stable system, that is, obtain the epoxy resin solution with autocatalytic activity electroless copper.
2. the collocation method of self-catalysis electroless copper epoxy resin solution as claimed in claim 1 is it is characterised in that described step
Active ion source in rapid A includes dissolving in acylate in organic solvent, metal carbonyl, metal alkoxide, acetyl
One or more of acetone coordination compound.
3. the collocation method of self-catalysis electroless copper epoxy resin solution as claimed in claim 1 is it is characterised in that described step
Organic solvent in rapid A is acetone, in butanone, hexamethylene, ethylene glycol, Polyethylene Glycol, isopropanol, oxolane, acetylacetone,2,4-pentanedione
One or more.
4. the collocation method of self-catalysis electroless copper epoxy resin solution as claimed in claim 1 is it is characterised in that described step
Rapid A also includes dispersant and/or diluent are added in obtained activator solution, is sufficiently stirred for, and forms final work
Property agent solution, described dispersant be one or more of ethylenediamine, dimethylformamide, dimethyl acetylamide, triethylamine.
5. the collocation method of self-catalysis electroless copper epoxy resin solution as claimed in claim 1 is it is characterised in that described solid
Change catalyst is tetraethylammonium bromide, dimethyl benzylamine, 2-ethyl-4-methylimidazole, 1- cyanoethyl -2- ethyl -4- methyl miaow
One or more of azoles, 2,4,6- tri- (dimethylaminomethyl) phenol, organic phosphine/bromo-complex；Described firming agent is first
Base tetrabydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic acid anhydride, triethylene four
One or more of amine, diethylaminopropylamine, m-diaminobenzene..
6. the collocation method of self-catalysis electroless copper epoxy resin solution as claimed in claim 1 is it is characterised in that described step
Epoxy resin in rapid B is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, (+)-2,3-Epoxy-1-propanol amine asphalt mixtures modified by epoxy resin
One or more of fat, linear aliphatic epoxy resin or alicyclic based epoxy resin.
7. the collocation method of self-catalysis electroless copper epoxy resin solution as claimed in claim 1 is it is characterised in that described step
Epoxy resin temperature in rapid B is 40～60 DEG C, and adding it to the velocity interval in firming agent is 2～5mL/min.
8. electroless copper plating method is it is characterised in that comprise the following steps：
A. toasted, by self-catalysis as claimed in any of claims 1 to 7 in one of claims after the substrate of cleaning printed circuit board
The self-catalysis electroless copper epoxy resin solution that the collocation method of copper plating resin solution is obtained is coated uniformly on substrate,
And it is placed on solidification certain time in baking oven；
B. take out rapidly in the substrate immersion micro-corrosion liquid after solidification step A being obtained, be placed in reducing solution, soak certain
Take out after time, and deionized water is cleaned；
C. substrate is placed in chemical bronze plating liquid, takes out after chemical plating 20～45min at a temperature of 30～45 DEG C, use deionization
Water is cleaned and is dried.
9. electroless copper plating method as claimed in claim 8 is it is characterised in that the micro-corrosion liquid in described step B is acetone, fourth
Ketone, hexamethylene, ethylene glycol, Polyethylene Glycol, isopropanol, oxolane, acetylacetone,2,4-pentanedione, chloroform or ethyl acetate；Described also
Originality solution is sodium borohydride, hydrazine hydrate, formaldehyde, ascorbic acid, sodium hydride, sodium thiosulfate.
10. electroless copper plating method as claimed in claim 8 is it is characterised in that electroless copper formula of liquid in described step C
For：Sodium hydroxide, 8g；Copper sulphate pentahydrate, 8g；Sodium potassium tartrate tetrahydrate, 8g；Edetate disodium, 8g；Polyethylene glycol 6000,
25mg；Potassium iodide, 5mg；Concentration is 37% formaldehyde, 6～8cm3；Water, 500cm3.
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| WO2023014524A1 (en) * | 2021-08-05 | 2023-02-09 | Macdermid Enthone Inc. | Compositions and methods for the electrodeposition of nanotwinned copper |
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| CN106824225B (en) * | 2017-02-20 | 2019-08-20 | 中国科学院深圳先进技术研究院 | A kind of PdCu alloy catalyst and the preparation method and application thereof |
| CN109487249B (en) * | 2019-01-03 | 2020-12-18 | 电子科技大学 | Chemical copper plating activator, preparation method thereof and method for manufacturing circuit by full addition based on activator |
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| CN102883543A (en) * | 2012-10-08 | 2013-01-16 | 复旦大学 | Method for manufacturing conducting circuit by additive process |
| CN103613289A (en) * | 2013-11-22 | 2014-03-05 | 华进半导体封装先导技术研发中心有限公司 | Method for electroless copper plating on glass substrate |
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| WO2006027947A1 (en) * | 2004-09-10 | 2006-03-16 | Nippon Mining & Metals Co., Ltd. | Electroless gold plating pretreatment agent and copper clad laminate for flexible board |
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| CN102883543A (en) * | 2012-10-08 | 2013-01-16 | 复旦大学 | Method for manufacturing conducting circuit by additive process |
| CN103613289A (en) * | 2013-11-22 | 2014-03-05 | 华进半导体封装先导技术研发中心有限公司 | Method for electroless copper plating on glass substrate |
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| WO2023014524A1 (en) * | 2021-08-05 | 2023-02-09 | Macdermid Enthone Inc. | Compositions and methods for the electrodeposition of nanotwinned copper |
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