CN106852005B - A method of printed circuit board is made using calixarenes - Google Patents
A method of printed circuit board is made using calixarenes Download PDFInfo
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- CN106852005B CN106852005B CN201710103611.2A CN201710103611A CN106852005B CN 106852005 B CN106852005 B CN 106852005B CN 201710103611 A CN201710103611 A CN 201710103611A CN 106852005 B CN106852005 B CN 106852005B
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- calixarenes
- circuit board
- printed circuit
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- substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1216—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by screen printing or stencil printing
- H05K3/1233—Methods or means for supplying the conductive material and for forcing it through the screen or stencil
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/14—Related to the order of processing steps
- H05K2203/1476—Same or similar kind of process performed in phases, e.g. coarse patterning followed by fine patterning
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention discloses it is a kind of using calixarenes production printed circuit board method comprising following steps: a) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and continue stirring can obtain calixarenes solution；B) under normal temperature and pressure, liquid copper slurry and calixarenes solution are separately added into the container with dispersal device, and continue to disperse, then discharge to obtain one-step print liquid；C) processing such as drill to substrate, cleaned, and substrate is placed on screen printer；D) in the screen printer that gained printed liquid is added, and one-step print liquid is embrocated to formation printing liquid layer on substrate；E) gained substrate is placed in baking box and is toasted, then printed circuit board can be obtained after natural cooling.The method feature of environmental protection using calixarenes production printed circuit board of the invention is strong, copper particle the can be improved adhesive force on substrate and reduces conducting wire impedance.
Description
Technical field
The present invention relates to a kind of manufacture field of printed circuit board, it is specifically a kind of not only there is good environmental-protecting performance but also
The method using calixarenes production printed circuit board for having excellent quality stability.
Background technique
With economic continuous development, printed circuit board is also increasingly wide in the application of the industries such as household electrical appliance, industrial electronic
It is general.Because printed circuit board has the extremely strong processing cost that electronic product can be greatly reduced, industrial reproducibility, the degree of automation and life
The higher advantage of efficiency is produced, so its depth is by vast electric appliance, the favor of electronics industry producer.However, existing printed circuit board
There are two great technological deficiencies for production process.It is process first, traditional printed circuit board generallys use Subtraction method,
Mainly it is made of processes such as cleaning, press mold, development, etching and stripings.Due to the Reusability industrial chemicals on substrate plate body, because
And the environmental contaminants of a large amount of heavy metal, high concentrated acid, alkali etc. can be generated in the process of printed circuit board.When above-mentioned
Ecological environment of the pollutant directly toward around can seriously destroy when extraneous discharge, belongs to so traditional printed circuit board produces
Heavily contaminated processing industry.Second, the technique of traditional Subtraction method production printed circuit board can not only consume a large amount of metal money
Source can also consume a large amount of energy, and need to carry out environmental protection treatment to waste material in following process.So Subtraction method adds
Work printed circuit board is a kind of industry of labour's highly dense, other than there is a problem of that the step of entirely processing is more,
Also need to carry out a degree of manpower operation in processing, cause the production cost of printed circuit board always cannot substantially under
Drop, and its processing efficiency is relatively low.
In order to solve the problems, such as that pollutant discharge amount is larger, occurs the silk-screen printing technique of circuit board currently on the market.
It prints the line map of electrically conductive ink to substrate using printing plate, and small copper particle is solidificated in electrically conductive ink by being electroplated
On, to form the conducting wire on substrate.As Chinese patent literature CN102612269A discloses a kind of all print printing electricity
The production method of road plate is printed the line map that electrically conductive ink is constituted to substrate using the principle of silk-screen printing, and is passed through
Electroplating line figure is adhered to copper particle on line map, to form conductive circuit diagram on substrate.Although this method can be from one
Determine to solve the problems, such as that pollutant largely discharges in degree, although although copper particle is still however, plating belongs to electrochemical process
It is to realize that it is fixed on substrate by the way of physical adherence, thus adhesive force of the copper particle on substrate is lower.Meanwhile copper
Simple substance can be directly exposed in the external world when being adhered to substrate, and the route of circuit board is caused to be easy to occur aoxidizing to fall off with copper particle
The case where, to considerably increase the impedance of route.Therefore, the adhesive force of copper particle and substrate how had not only been improved, but also can have been reduced
The impedance of route is always the significant technology issues of printed circuit board manufacture field.
In fact, occurring the feelings of conducting wire broken string due to manufacturing deficiency when in the manufacturing process of printed circuit board
Condition is frequent occurrence.Traditional solution is printed circuit board to be placed on independent benefit line machine, first removes the protection on route
Then oil strikes off the copper particle around at broken string, then carry out mending line operation.But traditional benefit line method equally will appear benefit
The copper particle lower problem of adhesive force on substrate again at line, and the operation for mending line needs individually to carry out, so as to cause printed circuit
The processing efficiency of plate declines to a great extent.
Summary of the invention
It is strong it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of feature of environmental protection and copper particle can be improved exist
The method using calixarenes production printed circuit board of adhesive force on substrate.
Another object of the present invention is to overcome the deficiencies of the prior art and provide a kind of conduction that can be effectively prevent on substrate
There is the method using calixarenes production printed circuit board aoxidized in route.
Goal of the invention of the invention is achieved in that a kind of method using calixarenes production printed circuit board, special
Sign is: the method for the production printed circuit board includes the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 5-30 minutes by mixing, and the mass percent of calixarenes in the solution is 1-20%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 400-900 revs/min of speed 10-40 minutes, then discharge to obtain one-step print liquid, one-step print
The mass ratio of copper particle and calixarenes is (2-8) in liquid: 1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 30-240 minutes at 100-200 DEG C, then natural cooling
The printed circuit board using calixarenes production can be obtained after to room temperature.
Furtherly, the calixarenes in step a be one of cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons or with
Arbitrary proportion mixing.
Furtherly, cup [4] aromatic hydrocarbons is 4- tert-butyl p tertButylcalixarene；Cup [6] aromatic hydrocarbons is to tert-butyl-calix [6] aromatic hydrocarbons；
Cup [8] aromatic hydrocarbons is to tert-butyl-calix [8] aromatic hydrocarbons.
Furtherly, the organic solvent in step a is one of toluene, dimethylbenzene or styrene or is mixed with arbitrary proportion
It closes.
Furtherly, after the completion of step e, at normal temperatures and pressures, calixarenes solution point obtained by liquid copper slurry and a step
Jia Ru not be in the container with dispersal device, and persistently disperse under 600-1200 revs/min of speed 20-60 minutes, then discharge
Secondary printing liquid is obtained, the mass ratio of copper particle and calixarenes is (9-15) in secondary printing liquid: 1；Printed circuit board is placed in again
On the screen printing table of screen printer, and secondary printing liquid is added into screen printer, two are carried out to printed circuit board according still further to line requirements
Secondary printing.
Furtherly, after the completion of secondary printing, gained substrate is placed in baking box, is toasted at 120-200 DEG C
100-300 minutes, then printed circuit board can be obtained after cooled to room temperature.
Furtherly, copper slurry is nanosized copper slurry in step b, and the partial size of copper particle is 50-90 nanometers.
The present invention improves the production technology of the printed circuit board of the prior art, and advantage is as follows:
1, in the method for the invention using calixarenes production printed circuit board, calixarenes is used as copper particle in base
Carrier on plate.Firstly, calixarenes have multidimensional can complexed active key, in addition to can with baseplate material occur complex reaction
Outside, moreover it is possible to the copper particle in copper slurry be complexed, form the connection structure of two-way complexing.The two-way chelation structure can make copper particle exist
It is persistently acted on by the complexing power of chemical bond rank on substrate, is truly realized copper particle being connected chemically on non-metal base plate,
To greatly improve adhesive force of the copper particle on substrate, avoids copper particle and occur the feelings to fall off on the route printed
Condition.Secondly, calixarenes itself has adjustable molecule cavity, it can be according to copper particle when generating complex reaction with copper particle
Particle size adjustment molecule cavity accommodation space, with eliminate between copper particle complexing when space steric effect, thus
Close-packed arrays of the copper particle on printing liquid layer are realized, uniform complex copper continuous phase is formed, it is online to greatly improve substrate
The electric conductivity on road.
2, in the method for the invention using calixarenes production printed circuit board, copper particle is on substrate in a manner of complexing
Structure is connected chemically with printing liquid layer formation.Firstly, this, which is connected chemically structure, can greatly improve copper particle in whole circuit board print
Utilization rate during system, effectively reduces the waste of copper particle, to reduce processing cost when circuit board printing.Secondly,
After being complexed with calixarenes, chemical reactivity declines to a great extent copper particle, so that effectively reducing copper particle is exposed to air
The oxidation reaction of middle generation avoids conducting wire that route is made to generate the phenomenon that impedance increases because of oxidation, to ensure conducting wire
The stability and reliability of work.
3, in the method for the invention using calixarenes production printed circuit board, printed liquid uses calixarenes solution and liquid
The dispersion mixing of state copper slurry makes printed liquid form the suspension system of copper particle.The system can promote copper particle in calixarenes
The uniformity of distribution, and printed liquid is made to constitute the multidimensional complexing environment between copper particle and calixarenes on substrate, it is effectively improved
Arranging density of the copper particle in unit area, to promote the electric conductivity of route.In addition, calixarenes solution can be to copper particle
Package action is generated, avoids copper particle from being directly exposed to the external world, to reduce the oxidation activity of copper particle, to reduce line
Road aoxidize it is dimmed, black phenomena such as generation.
It 4,, can be with after copper slurry is completed for printing in the method for the invention using calixarenes production printed circuit board
Secondary printing is carried out to substrate using copper particle content higher secondary printing liquid.Secondary printing can guarantee copper particle and printed liquid
The completeness of complexing, and copper particle cavity, the missing point etc. that generate in one-step print are repaired, exist so as to improve copper particle
Uniformity and compactness on substrate, improve the electric conductivity of route.
5, it in the method for the invention using calixarenes production printed circuit board, is starched using high concentration copper to printed circuit board
Carry out secondary printing.Firstly, the excessive copper particle and printed liquid starched by copper generate highdensity complex reaction, printed with repairing
The defects of open circuit that circuit board processed generates when processing, route defect, ensure that the complete of conducting wire on printed circuit board
Property and electric conductivity.Secondly, secondary printing can carry out on the screen printer of initial production, so in printing without to printing
Circuit board carries out the operation such as additional positioning, calibration, significantly reduces the difficulty of circuit mending, to effectively promote printing electricity
The processing efficiency of road plate.
Specific embodiment
Method using calixarenes production printed circuit board of the invention, it is characterised in that: the production printed circuit board
Method include the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 5-30 minutes by mixing, and the mass percent of calixarenes in the solution is 1-20%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 400-900 revs/min of speed 10-40 minutes, then discharge to obtain one-step print liquid, one-step print
The mass ratio of copper particle and calixarenes is (2-8) in liquid: 1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 30-240 minutes at 100-200 DEG C, then natural cooling
The printed circuit board using calixarenes production can be obtained after to room temperature.
Wherein, the calixarenes in step a is for one of cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons or with any
Ratio mixing.The multidimensional having using calixarenes can complexed active structure, make it can be respectively and in baseplate material and copper slurry
Complex reaction occurs for copper particle, is formed using calixarenes as the two-way complexing connection structure of basic point.The two-way chelation structure makes copper particle
Son is persistently acted on by the complexing power of chemical bond rank on substrate, realizes copper particle being connected chemically on non-metal base plate,
To promote adhesive force of the copper particle on substrate, copper particle is avoided the case where falling off on the route printed.This
Outside, it since cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons itself have adjustable molecule cavity, is produced with copper particle
The accommodation space that molecule cavity can be adjusted when raw complex reaction according to the particle size of copper particle, is printing to realize copper particle
Close-packed arrays on brush liquid layer form uniform complex copper continuous phase, improve the electric conductivity of route on substrate.In the present invention
In, cup [4] aromatic hydrocarbons is 4- tert-butyl p tertButylcalixarene；Cup [6] aromatic hydrocarbons is to tert-butyl-calix [6] aromatic hydrocarbons；Cup [8] aromatic hydrocarbons is to uncle
Butyl cup [8] aromatic hydrocarbons.Said components have using phenyl ring as the symmetrical chelation structure of basic point, be effectively improved its respectively with baseplate material
With the stability of copper particle complexing.
In addition, the organic solvent in step a is one of toluene, dimethylbenzene or styrene or is mixed with arbitrary proportion.
Above-mentioned solvent and calixarenes have approximate benzene ring structure, outstanding dissolution can be generated to calixarenes according to similar compatibility principle
Effect, to improve uniformity of the calixarenes in printed liquid.
Liquid copper slurry and calixarenes solution have been carried out dispersion mixing by step b of the invention, and printed liquid is made to form copper particle
The suspension system of son.The system can promote the uniformity that copper particle is distributed in calixarenes, and constitute printed liquid on substrate
Environment is complexed in multidimensional between copper particle and calixarenes, arranging density of the copper particle in unit area is effectively improved, to mention
Rise the electric conductivity of route.In addition, calixarenes solution can generate package action to copper particle, copper particle is avoided to be directly exposed to outer
Boundary, to reduce the oxidation activity of copper particle, thus reduce route aoxidize it is dimmed, black phenomena such as generation.
After the completion of step e of the invention, under normal temperature and pressure environment, calixarenes obtained by liquid copper slurry and a step
Solution is separately added into the container with dispersal device, and persistently disperses 20-60 minutes under 600-1200 revs/min of speed, so
After discharge to obtain secondary printing liquid, the mass ratio of copper particle and calixarenes is (9-15) in secondary printing liquid: 1；Again printed circuit
Plate is placed on the screen printing table of screen printer, and secondary printing liquid is added into screen printer, according still further to line requirements to printed circuit board
Carry out secondary printing.By copper particle and the ratio of calixarenes using excessive complexing mode, enable copper particle as far as possible with cup
Aromatic hydrocarbons generate complex reaction, thus promoted complexing after the completion of copper particle than table density, to the copper particle generated in one-step print
Sub- cavity, missing point etc. are repaired, and uniformity and compactness of the copper particle on substrate are improved.
After the completion of secondary printing, gained substrate can be placed in baking box, and toast 100-300 at 120-200 DEG C
Minute, then printed circuit board can be obtained after cooled to room temperature.By promoting the basal temperature and baking time of baking, can mention
The complex reaction activity for rising copper particle and calixarenes in copper slurry makes that density height, fireballing network occur in entire complex system
Reaction is closed, and the space steric effect between copper particle in complexing can be eliminated, further promotes copper particle on printing liquid layer
The compactness of arrangement.
In addition, present invention utilizes high concentration copper slurries to carry out secondary printing to printed circuit board.The excess copper starched by copper
Particle and printed liquid generate highdensity complex reaction, to repair the open circuit, the route defect that generate in printed circuit board processing
The defects of, ensure that the integrality and electric conductivity of conducting wire on printed circuit board.Meanwhile secondary printing can be first
Begin to carry out on the screen printer produced, so in printing without carrying out the operation such as additional positioning, calibration to printed circuit board plate,
The difficulty of circuit mending is significantly reduced, to effectively promote the processing efficiency of printed circuit board.
In step e of the invention, nanosized copper slurry is can be used in copper slurry, and the partial size of copper particle is 50-90 nanometers.Upper
It states under particle size range, copper particle has extremely outstanding ductility, and has excellent mechanical performance.In addition, the particle size range
Under copper particle be also equipped with the advantages that deformation is uniform, bonding strength is high, to assign route good inclusion characteristic, can improve logical
Bonding strength of the electric line on substrate.
Resistivity, adhesive force are carried out respectively to printed circuit board made by the use present invention according to IPC-TM-650 standard
Tested with welding performance, printed circuit board made from the method for this utilization invention in the conductive under of same units length,
Resistivity is 1.5-12 Ω .mm2/m；3M seccotine adhesive force test result is without there is peeling；And in immersed solder test
Phenomena such as its wetting state is well and blisters, is layered, burns and changes colour without appearance after 250-280 DEG C of heating.
The present invention is described in detail using each embodiment of the method for calixarenes production printed circuit board below, but
Therefore do not limit the invention in the scope of embodiments:
Embodiment 1
The method of production printed circuit board of the invention includes the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 5 minutes by mixing, and the mass percent of calixarenes in the solution is 1%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 400 revs/min of speed 10 minutes, then discharge to obtain one-step print liquid, copper particle in one-step print liquid
The mass ratio of son and calixarenes is 2:1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 30 minutes at 100 DEG C, then after cooled to room temperature
The printed circuit board using calixarenes production can be obtained.
Wherein the calixarenes in step a is cup [4] aromatic hydrocarbons, and 4- tert-butyl p tertButylcalixarene can be used in cup [4] aromatic hydrocarbons；And
Toluene can be used in organic solvent in step a.
In addition, after the completion of step e, under normal temperature and pressure environment, calixarenes solution point obtained by liquid copper slurry and a step
Jia Ru not be in the container with dispersal device, and persistently disperse under 600 revs/min of speed 20 minutes, then discharge to obtain secondary print
Brush liquid, the mass ratio of copper particle and calixarenes is 9:1 in secondary printing liquid；Printed circuit board is placed in again the screen printing table of screen printer
On, and secondary printing liquid is added into screen printer, secondary printing is carried out to printed circuit board according still further to line requirements.And when secondary
After being completed for printing, gained substrate is placed in baking box, is toasted 100 minutes at 120 DEG C, then after cooled to room temperature
Obtain printed circuit board.
In addition, copper slurry is nanosized copper slurry in step e, the partial size of copper particle is 90 nanometers.
Resistivity, adhesive force are carried out respectively to printed circuit board made by the use present invention according to IPC-TM-650 standard
Tested with welding performance, printed circuit board made from the method for this utilization invention in the conductive under of same units length,
Resistivity is 12 Ω .mm2/m；3M seccotine adhesive force test result is without there is peeling；And its profit in immersed solder test
Phenomena such as wet condition is well and blisters, is layered, burns and changes colour without appearance after 250 DEG C of heating.
Embodiment 2
The method of production printed circuit board of the invention includes the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 30 minutes by mixing, and the mass percent of calixarenes in the solution is 20%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 900 revs/min of speed 40 minutes, then discharge to obtain one-step print liquid, copper particle in one-step print liquid
The mass ratio of son and calixarenes is 8:1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 240 minutes at 200 DEG C, then after cooled to room temperature
The printed circuit board using calixarenes production can be obtained.
Wherein the calixarenes in step a is the arbitrary proportion mixture of cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons.
Specifically, cup [4] aromatic hydrocarbons is 4- tert-butyl p tertButylcalixarene；Cup [6] aromatic hydrocarbons is to tert-butyl-calix [6] aromatic hydrocarbons；Cup [8] aromatic hydrocarbons be
To tert-butyl-calix [8] aromatic hydrocarbons.And the organic solvent in step a is the arbitrary proportion mixture of toluene, dimethylbenzene or styrene.
In addition, after the completion of step e, under normal temperature and pressure environment, calixarenes solution point obtained by liquid copper slurry and a step
Jia Ru not be in the container with dispersal device, and persistently disperse under 1200 revs/min of speed 60 minutes, then discharge to obtain secondary print
Brush liquid, the mass ratio of copper particle and calixarenes is 15:1 in secondary printing liquid；Printed circuit board is placed in again the silk-screen of screen printer
On platform, and secondary printing liquid is added into screen printer, secondary printing is carried out to printed circuit board according still further to line requirements.And when two
It is secondary be completed for printing after, gained substrate is placed in baking box, is toasted 300 minutes at 200 DEG C, then after cooled to room temperature i.e.
Printed circuit board can be obtained.
In addition, copper slurry is nanosized copper slurry in step e, the partial size of copper particle is 50 nanometers.
Resistivity, adhesive force are carried out respectively to printed circuit board made by the use present invention according to IPC-TM-650 standard
Tested with welding performance, printed circuit board made from the method for this utilization invention in the conductive under of same units length,
Resistivity is 1.5 Ω .mm2/m；3M seccotine adhesive force test result is without there is peeling；And its profit in immersed solder test
Phenomena such as wet condition is well and blisters, is layered, burns and changes colour without appearance after 280 DEG C of heating.
Embodiment 3
The method of production printed circuit board of the invention includes the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 15 minutes by mixing, and the mass percent of calixarenes in the solution is 6%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 500 revs/min of speed 15 minutes, then discharge to obtain one-step print liquid, copper particle in one-step print liquid
The mass ratio of son and calixarenes is 3:1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 80 minutes at 140 DEG C, then after cooled to room temperature
The printed circuit board using calixarenes production can be obtained.
Wherein the calixarenes in step a is the arbitrary proportion mixture of cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons.Specifically, cup
[6] aromatic hydrocarbons is to tert-butyl-calix [6] aromatic hydrocarbons；Cup [8] aromatic hydrocarbons is to tert-butyl-calix [8] aromatic hydrocarbons.And the organic solvent in step a
For toluene, the arbitrary proportion mixture of dimethylbenzene.
In addition, after the completion of step e, under normal temperature and pressure environment, calixarenes solution point obtained by liquid copper slurry and a step
Jia Ru not be in the container with dispersal device, and persistently disperse under 700 revs/min of speed 30 minutes, then discharge to obtain secondary print
Brush liquid, the mass ratio of copper particle and calixarenes is 11:1 in secondary printing liquid；Printed circuit board is placed in again the silk-screen of screen printer
On platform, and secondary printing liquid is added into screen printer, secondary printing is carried out to printed circuit board according still further to line requirements.And when two
It is secondary be completed for printing after, gained substrate is placed in baking box, is toasted 150 minutes at 140 DEG C, then after cooled to room temperature i.e.
Printed circuit board can be obtained.
In addition, copper slurry is nanosized copper slurry in step e, the partial size of copper particle is 80 nanometers.
Resistivity, adhesive force are carried out respectively to printed circuit board made by the use present invention according to IPC-TM-650 standard
Tested with welding performance, printed circuit board made from the method for this utilization invention in the conductive under of same units length,
Resistivity is 10 Ω .mm2/m；3M seccotine adhesive force test result is without there is peeling；And its profit in immersed solder test
Phenomena such as wet condition is well and blisters, is layered, burns and changes colour without appearance after 260 DEG C of heating.
Embodiment 4
The method of production printed circuit board of the invention includes the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 20 minutes by mixing, and the mass percent of calixarenes in the solution is 12%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 700 revs/min of speed 25 minutes, then discharge to obtain one-step print liquid, copper particle in one-step print liquid
The mass ratio of son and calixarenes is 5:1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 160 minutes at 150 DEG C, then after cooled to room temperature
The printed circuit board using calixarenes production can be obtained.
Wherein the calixarenes in step a is the arbitrary proportion mixture of cup [4] aromatic hydrocarbons and cup [8] aromatic hydrocarbons.Specifically, cup
[4] aromatic hydrocarbons is 4- tert-butyl p tertButylcalixarene；Cup [8] aromatic hydrocarbons is to tert-butyl-calix [8] aromatic hydrocarbons.And the organic solvent in step a
For the arbitrary proportion mixture of toluene and styrene.
In addition, after the completion of step e, under normal temperature and pressure environment, calixarenes solution point obtained by liquid copper slurry and a step
Jia Ru not be in the container with dispersal device, and persistently disperse under 900 revs/min of speed 40 minutes, then discharge to obtain secondary print
Brush liquid, the mass ratio of copper particle and calixarenes is 12:1 in secondary printing liquid；Printed circuit board is placed in again the silk-screen of screen printer
On platform, and secondary printing liquid is added into screen printer, secondary printing is carried out to printed circuit board according still further to line requirements.And when two
It is secondary be completed for printing after, gained substrate is placed in baking box, is toasted 200 minutes at 180 DEG C, then after cooled to room temperature i.e.
Printed circuit board can be obtained.
In addition, copper slurry is nanosized copper slurry in step e, the partial size of copper particle is 70 nanometers.
Resistivity, adhesive force are carried out respectively to printed circuit board made by the use present invention according to IPC-TM-650 standard
Tested with welding performance, printed circuit board made from the method for this utilization invention in the conductive under of same units length,
Resistivity is 8 Ω .mm2/m；3M seccotine adhesive force test result is without there is peeling；And its wetting in immersed solder test
Phenomena such as state is well and blisters, is layered, burns and changes colour without appearance after 270 DEG C of heating.
Embodiment 5
The method of production printed circuit board of the invention includes the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and is persistently stirred
Calixarenes solution can be obtained for 25 minutes by mixing, and the mass percent of calixarenes in the solution is 16%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the appearance with dispersal device
In device, and persistently disperse under 800 revs/min of speed 35 minutes, then discharge to obtain one-step print liquid, copper particle in one-step print liquid
The mass ratio of son and calixarenes is 7:1；
(2) substrate pre-treatment
C) processing such as drill to substrate according to line requirements, cleaned, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated according to line requirements
Printing liquid layer is formed on to substrate；
E) substrate obtained by Step d is placed in baking box, is toasted 220 minutes at 180 DEG C, then after cooled to room temperature
The printed circuit board using calixarenes production can be obtained.
Wherein the calixarenes in step a is the arbitrary proportion mixture of cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons.
Specifically, cup [4] aromatic hydrocarbons is 4- tert-butyl p tertButylcalixarene；Cup [6] aromatic hydrocarbons is to tert-butyl-calix [6] aromatic hydrocarbons；Cup [8] aromatic hydrocarbons be
To tert-butyl-calix [8] aromatic hydrocarbons.And the organic solvent in step a is the arbitrary proportion mixture of toluene, dimethylbenzene or styrene.
In addition, after the completion of step e, under normal temperature and pressure environment, calixarenes solution point obtained by liquid copper slurry and a step
Jia Ru not be in the container with dispersal device, and persistently disperse under 1000 revs/min of speed 50 minutes, then discharge to obtain secondary print
Brush liquid, the mass ratio of copper particle and calixarenes is 14:1 in secondary printing liquid；Printed circuit board is placed in again the silk-screen of screen printer
On platform, and secondary printing liquid is added into screen printer, secondary printing is carried out to printed circuit board according still further to line requirements.And when two
It is secondary be completed for printing after, gained substrate is placed in baking box, is toasted 260 minutes at 190 DEG C, then after cooled to room temperature i.e.
Printed circuit board can be obtained.
In addition, copper slurry is nanosized copper slurry in step e, the partial size of copper particle is 60 nanometers.
Resistivity, adhesive force are carried out respectively to printed circuit board made by the use present invention according to IPC-TM-650 standard
Tested with welding performance, printed circuit board made from the method for this utilization invention in the conductive under of same units length,
Resistivity is 6 Ω .mm2/m；3M seccotine adhesive force test result is without there is peeling；And its wetting in immersed solder test
Phenomena such as state is well and blisters, is layered, burns and changes colour without appearance after 280 DEG C of heating.
Claims (7)
1. a kind of method using calixarenes production printed circuit board, it is characterised in that: the method for the production printed circuit board
Include the following steps:
(1) preparation of printed liquid
A) under normal temperature and pressure, calixarenes and organic solvent are separately added into the container with agitating device, and continue to stir 5-
Calixarenes solution can be obtained within 30 minutes, the mass percent of calixarenes in the solution is 1-20%；
B) under normal temperature and pressure, calixarenes solution obtained by liquid copper slurry and a step is separately added into the container with dispersal device,
And persistently disperse under 400-900 revs/min of speed 10-40 minutes, then discharge to obtain one-step print liquid, copper in one-step print liquid
The mass ratio of particle and calixarenes is (2-8): 1；
(2) substrate pre-treatment
C) it is drilled according to line requirements to substrate, cleaning treatment, and substrate is placed on the screen printing table of screen printer；
(3) the route printing of substrate
D) printed liquid obtained by b step is added in the screen printer of step c, and one-step print liquid is embrocated to base according to line requirements
Printing liquid layer is formed on plate；
E) substrate obtained by Step d is placed in baking box, is toasted 30-240 minutes at 100-200 DEG C, then naturally cool to room
The printed circuit board using calixarenes production can be obtained after temperature.
2. according to claim 1 using the method for calixarenes production printed circuit board, it is characterised in that: in the step a
Calixarenes be one of cup [4] aromatic hydrocarbons, cup [6] aromatic hydrocarbons and cup [8] aromatic hydrocarbons or mixed with arbitrary proportion.
3. according to claim 2 using the method for calixarenes production printed circuit board, it is characterised in that: cup [4] virtue
Hydrocarbon is 4- tert-butyl p tertButylcalixarene；Cup [6] aromatic hydrocarbons is to tert-butyl-calix [6] aromatic hydrocarbons；Cup [8] aromatic hydrocarbons is to tert-butyl-calix [8] virtue
Hydrocarbon.
4. according to claim 1 using the method for calixarenes production printed circuit board, it is characterised in that: in the step a
Organic solvent be one of toluene, dimethylbenzene or styrene or mixed with arbitrary proportion.
5. according to claim 1 using the method for calixarenes production printed circuit board, it is characterised in that: the step e is complete
Calixarenes solution obtained by liquid copper slurry and a step is separately added into the container with dispersal device at normal temperatures and pressures by Cheng Hou
In, and persistently disperse under 600-1200 revs/min of speed 20-60 minutes, then discharge to obtain secondary printing liquid, secondary printing liquid
The mass ratio of middle copper particle and calixarenes is (9-15): 1；Printed circuit board is placed on the screen printing table of screen printer again, and past silk
Secondary printing liquid is added in print machine, secondary printing is carried out to printed circuit board according still further to line requirements.
6. according to claim 5 using the method for calixarenes production printed circuit board, it is characterised in that: the secondary printing
After the completion, gained substrate is placed in baking box, is toasted 100-300 minutes at 120-200 DEG C, then after cooled to room temperature
Printed circuit board can be obtained.
7. according to claim 1 using the method for calixarenes production printed circuit board, it is characterised in that: in the step e
Copper slurry is nanosized copper slurry, and the partial size of copper particle is 50-90 nanometers.
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|---|---|---|---|---|
| US4642362A (en) * | 1984-01-30 | 1987-02-10 | Loctite (Ireland) Limited | Polymer bound calixarenes |
| CN101525745A (en) * | 2009-04-03 | 2009-09-09 | 四川大学 | Metal surface treatment agent and printed wiring board with protecting film formed thereby |
| CN102414343A (en) * | 2009-04-30 | 2012-04-11 | 法国原子能及替代能源委员会 | Method for preparing a metallised substrate, the resulting substrate and the uses thereof |
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|---|---|---|---|---|
| JP5926601B2 (en) * | 2011-04-13 | 2016-05-25 | 積水化学工業株式会社 | Anisotropic conductive material and connection structure |
| JP5810798B2 (en) * | 2011-09-22 | 2015-11-11 | 大日本印刷株式会社 | Hydraulic transfer film and method for producing decorative molded product using the same |
| JP5842778B2 (en) * | 2011-09-29 | 2016-01-13 | Jsr株式会社 | Pattern formation method |
| JP2014024977A (en) * | 2012-07-27 | 2014-02-06 | Dic Corp | Curable resin composition, cured product and printed wiring board |
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2017
- 2017-02-24 CN CN201710103611.2A patent/CN106852005B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4642362A (en) * | 1984-01-30 | 1987-02-10 | Loctite (Ireland) Limited | Polymer bound calixarenes |
| CN101525745A (en) * | 2009-04-03 | 2009-09-09 | 四川大学 | Metal surface treatment agent and printed wiring board with protecting film formed thereby |
| CN102414343A (en) * | 2009-04-30 | 2012-04-11 | 法国原子能及替代能源委员会 | Method for preparing a metallised substrate, the resulting substrate and the uses thereof |
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