CN104244587B - The preparation method and thermosetting spray solution of stereo circuit - Google Patents
The preparation method and thermosetting spray solution of stereo circuit Download PDFInfo
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- CN104244587B CN104244587B CN201410182086.4A CN201410182086A CN104244587B CN 104244587 B CN104244587 B CN 104244587B CN 201410182086 A CN201410182086 A CN 201410182086A CN 104244587 B CN104244587 B CN 104244587B
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Abstract
The invention discloses a kind of preparation method of stereo circuit, comprise the following steps：Prototype is generated by selective laser sintering method；Spray treatment is carried out to the prototype surface with the thermosetting spray solution containing soluble metal complex compound and solidified, forming surface can be by the overlay film of laser activation；Predetermined selective scanning is carried out to the overlay film to form surface active region with laser；Conducting wire is formed in the surface active region by chemical plating.On the basis of application selective laser sintering method obtains prototype, using thermosetting solution in prototype surface coating and with laser activation, both the limitation for having overcome traditional SLS rapidoprints to bring application, it can realize that the complicated matrix in surface is molded without being limited by profile again, effectively meet the requirement of laser activation and the shaping of conducting wire quick Fabrication.
Description
Technical field
The present invention relates to a kind of preparation method of stereo circuit and thermosetting spray solution.
Background technology
For electronic apparatus and electronic product manufacturing process and corresponding material technology, the direction of pursuit is flexible, environmental protection,
Quickly, save.Industry develops referred to as 3D-MID (Three-dimensional moulded interconnect device
Or electronic assemblies) technology, the technology is molded accurate and close conductive pattern, electronics in plastic surface
Component can be directly welded on plastic shell or inner casing, form the electronic apparatus and electromechanical integration of no printed circuit board (PCB)
Product.The technology is applied to the making of stereo circuit, is that electric equipment products and electronic product save circuit space, realizes circuit
Flexibility manufacture.Its major domain is：Communication Equipment antenna, consumer electronics, medicine equipment etc. have to space requirement, accuracy
The field of high requirement.
Traditional 3D-MID technological process mainly includes three steps：Step 1, using a kind of laser plastic material injection or
It is cast into plastic parts；Step 2, laser equipment press the designed cad file of user, scan plastic parts, form conductive pattern, this
Step turns into laser treatment or laser activation；Step 3, the plastic parts chemical plating by laser treatment thicken metal level.
Traditional 3D-MID technologies manufacture circuit carrier by the way of injection, are limited by carrier profile, are molded simultaneously
Part molding time is longer, is unfavorable for rapid processing and the test of quick MID devices.
Another moulding process, laser sintered (SLS) technology of conventional selective mainly include：Matrix model by section at
Reason import equipment in be processed, laser selective agglomerating plant Layered manufacturing hierarchical model and under hot melt state complete layer it
Between combination, be sequentially overlapped the making for completing whole prototype.
The application of SLS technologies allows complex model to realize rapid shaping, and various aspects of performance reaches moulding standard,
Molding part can be used directly.
However, traditional SLS products can not meet the requirement of laser surface activation, while also being capable of not effective integration SLS
The laser equipment of technique, so the product containing circuit inside plastic parts can not be manufactured by traditional SLS technologies.
The content of the invention
It is a primary object of the present invention to overcome the deficiencies in the prior art, there is provided a kind of making side of new stereo circuit
Method.
Another object is to provide the thermosetting spray that a kind of preparation method for the stereo circuit can obtain excellent effect
Apply solution.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of stereo circuit, comprises the following steps：
Step 1: prototype is generated by selective laser sintering method；
Step 2: the prototype surface is sprayed with the thermosetting spray solution containing soluble metal complex compound
Handle and solidify, forming surface can be by the overlay film of laser activation；
Step 3: predetermined selective scanning is carried out to the overlay film to form surface active region with laser；
Step 4: conducting wire is formed in the surface active region by chemical plating.
Preferably, the thermosetting spray solution contains following component in parts by mass：(1) thermoset carrier rubber master batch 35~
65 mass parts；(2) mass parts of amino resins 15~30；(3) mass parts of metal complex 0.5~10；(4) inorganic functional fillers 15
~25 mass parts；(5) mass parts of aromatic solvent 3~5；(6) mass parts of DAA 3~5；(7) mass parts of dimethylbenzene 2~4；
(8) mass parts of defoamer 0.1~0.7；(9) mass parts of dispersant 0.1~2；(10) mass parts of levelling agent 0.1~1.
Preferably, the metal complex is the complex compound of copper, aluminium, zinc or nickel.
Preferably, in the step 1, the carbon dioxide infrared laser that wavelength is 10W~40W for 10.6 μm, power is used
Device carries out selective laser sintering, and wherein 3~5m/s of laser scan rate, spot diameter 0.5mm, X, Y, Z axis processing, which is shunk, mends
The rate X of repaying is 2.85~3.82%, Y is 2.85~3.82%, Z (0) is 2.10~3.22%, Z (300) is 1.47~2.44%,
Wherein Z (0) refers to the shrinkage-compensating rate in Z axis coordinate 0mm positions, and Z (300) refers to the shrinkage-compensating in Z axis coordinate 300mm positions
Rate, Z-direction remainder layer shrinkage factor according to Z (0), Z (300) value linearly rule of constant concentration be distributed, laser facula compensating parameter be 0.15~
0.35mm。
Preferably, in the step 3, it for the laser equipment or power that 10~40W, wavelength are 10.6 μm is 3 to use power
~10W, the laser equipment that wavelength is 1060~1090nm carry out laser scanning, line width 0.1mm or so, minimum spacing
0.2mm or so.It is highly preferred that the laser equipment has X/Y scanning galvanometers and is arranged in the Z axis perpendicular to surface to be activated
It is upper varifocal.
Preferably, in the step 3, surface laser activates and is maintained at 20 to the recession thickness on the prototype surface~
25 μm or so.
Preferably, in the step 4, also include carrying out oil removing to the surface of the prototype before chemical plating is carried out
With the stable processing of immersion.It is highly preferred that the stable processing of immersion is soaked at room temperature using the aqueous solution containing 10% formaldehyde
1min。
Preferably, the oil removing removes oil formula, wherein sodium hydroxide 100g/L using following, tertiary sodium phosphate 166.6g/L,
Sodium carbonate 100g/L, and detergent 16.6g/L.
Preferably, chemical plating uses following electroplate liquid formulation, wherein containing copper sulphate 10g/L, potassium sodium tartrate 50g/L, hydrogen
10~12g/L of sodium oxide molybdena, sodium carbonate 5g/L, nickel chloride 1g/L, and 10~15ml/L of formaldehyde.
A kind of thermosetting spray solution of preparation method for the stereo circuit, the thermosetting spray solution press matter
Amount part meter contains following component：(1) mass parts of thermoset carrier rubber master batch 35~65；(2) mass parts of amino resins 15~30；(3)
The mass parts of metal complex 0.5~10；(4) mass parts of inorganic functional fillers 15~25；(5) mass parts of aromatic solvent 3~5；(6)
The mass parts of DAA 3~5；(7) mass parts of dimethylbenzene 2~4；(8) mass parts of defoamer 0.1~0.7；(9) dispersant 0.1~
2 mass parts；(10) mass parts of levelling agent 0.1~1.
The advantageous effects of the present invention：
The present invention uses SLS technology rapid shaping prototypes, coats prototype surface with thermosetting spray solution, and pass through
Laser, through chemical plating, is completed stereo circuit and made, the preparation method effectively improves traditional MID and SLS to overlay film surface active
The deficiency of technique, using thermosetting solution in prototype surface coating and with laser activation, overcome traditional SLS rapidoprints corresponding
With the limitation brought, effectively meet laser activation and conducting wire forming requirements, meet part for conductive, heat conductivility need
Ask.Particularly, the present invention is on the basis of SLS techniques form prototype, by the way of surface spraying overlay film and laser activation,
The application of existing SLS technologies is extended, had both overcome limitation of the SLS technologies on material, overcomes traditional MID technologies adding again
Limitation in work profile and on shaping speed.On the one hand, the present invention may replace traditional MID Shooting Techniques and obtain preferably quick
Machine-shaping effect, on the other hand, surface coating activation method proposed by the present invention cause application SLS techniques on the basis of,
Stereo circuit making can be achieved not changing original rapidoprint, and realize the surface metalation of quick prototype.This hair
The advantages of bright this surface coating activating process, is embodied in：(1) quick Fabrication of stereo circuit, fabrication cycle are short；(2)
The complicated matrix shaping in surface is realized, is not limited by profile；(3) processing is flexible, and surface coating is controllable.
The present invention, which makes stereo circuit, has the advantages of traditional MID technologies are with SLS rapid shaping techniques, but eliminates each
From the shortcomings that, industry popularization cost can be reduced, and the end product quality of three-dimensional circuit manufacturing process is optimized
And there is superiority of effectiveness, the development of rapid laser-shaping technique will be greatly facilitated.As new stereo circuit manufacture craft, sheet
Invent and provide environmentally friendly, environment-friendly, flexible intelligent manufacture method for optical, mechanical and electronic integration product, be widely portable to automobile,
The electronic circuit production in the fields such as Aero-Space, Industry Control.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method embodiment of stereo circuit of the present invention.
Embodiment
Embodiments of the invention are elaborated below in conjunction with accompanying drawing.It is emphasized that the description below is only to show
Example property, the scope being not intended to be limiting of the invention and its application.
In some embodiments, a kind of preparation method of stereo circuit is as shown in figure 1, comprise the following steps.
Step 1, pass through selective laser sintering SLS methods generate prototype.
The technological parameter that laser selective sintering prepares prototype is as follows：
Prototype is manufactured using laser selective agglomerating plant, 10.6 μm of wavelength, the two of power 10W~40W can be used
Carbonoxide infrared laser shrinks as sintered source, 3~5m/s of laser scan rate, spot diameter 0.5mm, X, Y, Z axis processing
Cancellation ratio X is 2.85~3.82%, Y is 2.85~3.82%, Z (0) is 2.10~3.22%, Z (300) be 1.47~
2.44%, wherein Z (0) refer to the shrinkage-compensating rate in Z axis coordinate 0mm positions, and Z (300) refers to the receipts in Z axis coordinate 300mm positions
Contracting cancellation ratio, Z-direction remainder layer shrinkage factor are distributed according to Z (0), Z (300) value linearly rule of constant concentration, and laser facula compensating parameter is
0.15~0.35mm.
After prototype machines, the powder of prototype surface attachment can be cleared up by post processing modes such as sandblasting, water mills.
Step 2, with the thermosetting spray solution containing soluble metal complex compound the prototype surface is sprayed
Handle and solidify, forming surface can be by the overlay film of laser activation.
The application of traditional SLS products and performance are limited by material, by SLS prototype surface spraying covering materials
This defect can be made up so that the processing of MID products is not limited by SLS technology current materials.The thermosetting of spraying covers
Coating solution is attached to SLS prototypes, therefore can need not adjust traditional SLS material components so that traditional SLS technologies can not be by
Existing moulding material limits and is used to manufacture stereo circuit matrix, only need to be by prototype surface spraying thermosetting solution
The surface for completing prototype is modified link.
Have soluble metal complex compound (modified metal compound) in thermosetting solution, metal complex can be copper, aluminium,
The complex compound of zinc, nickel etc., thinner, levelling agent, metal reduction adjuvant can also be included.In a kind of preferred embodiment,
Contain in thermosetting solution：(1) thermoset carrier rubber master batch, the mass parts of solution 35~65 are accounted for；(2) amino resins, account for solution 15~
30 mass parts；(3) metal complex, the mass parts of solution 0.5~10 are accounted for；(4) inorganic functional fillers, the mass of solution 15~25 is accounted for
Part；(5) aromatic solvent, the mass parts of solution 3~5 are accounted for；(6) DAA, solution 3-5 mass parts are accounted for；(7) dimethylbenzene, solution 2 is accounted for
~4 mass parts；(8) defoamer, the mass parts of solution 0.1~0.7 are accounted for；(9) dispersant, the mass parts of solution 0.1~2 are accounted for；(10) flow
Flat agent, account for the mass parts of solution 0.1~1.Thermosetting solution uniformly after mixing, can use 0.5~1mm bores pneumatic spray gun to carry out table
Face sprays overlay film.
In subsequent process, the material of removal coated metal complex compound is activated by laser surface can make metal ion Cheng You
Amorph, then generate surface conductive layer with chemical plating solution.Make metal complex that there is above-mentioned preferred content, it is plated that chemistry can be optimized
Metal deposition rates in journey (content higher will make metal deposition rates slack-off).
Inorganic functional fillers can be acrylic acid or epoxy resin, for filling by selective laser sintering process principle institute
Increase case hardness after caused rough surface, solidification.
Step 3, with laser predetermined selective scanning is carried out to the overlay film to form surface active region.
Laser equipment and the technological parameter of laser scanning overlay film prototype are as follows：
Laser equipment, preferably 10~40W of power, the laser machine of 10.6 μm of wavelength, or 3~10W of power, wavelength can be used
1060~1090nm laser machine.Preferably, line width 0.1mm or so, minimum spacing 0.2mm or so.Laser instantaneous energy
When being pyrolyzed threshold value higher than metal complex in surface coating layer so that metal complex decomposes and produces metal ion.
Preferably, surface laser activation is maintained at 20~25 μm or so to the recession thickness on prototype surface.Preferably, swash
Ray machine possesses Z axis zoom function, adapts to the characteristics of plastic surface is uneven, adjust automatically so that spot size and circularity are not
Become.
In preferred embodiment, laser chemistry equipment uses X/Y vibration mirror scannings, has rotatable platform pedestal, has
Laser Z axis zoom function, rapidly and accurately complete the selective area surface active to three-dimensional prototype part.
After laser surface activation process, prototype surface completes coarsening process, metal occurs on prototype surface
Complex compound thin layer.
Step 4, by chemical plating circuit moulding process, form conducting wire in the surface active region.
By change depositing process produce conductive copper layer, by oil removing, stably, plating process, ultimately form 10~20 μ m-thicks
The conductive copper layer of degree.There is the situation of particular/special requirement to copper layer thickness, the duration that can be plated according to actual adjustmentization, or subsequently through
The mode of plating thickeies conductive layer.
(1) oil removing：It is preferred that to go oil formula to slough prototype surface grease shown in table 1, its surface tension is reduced, assigns it
Surface hydrophilicity；
The prototype surface alkalinty of table 1 removes oil formula
| Component | Content |
| Sodium hydroxide | 100g/L |
| Tertiary sodium phosphate | 166.6g/L |
| Sodium carbonate | 100g/L |
| Detergent | 16.6g/L |
(2) immersion is stable：Because film covering solution with the addition of the metal ion needed for reaction, thus without it is traditional be sensitized, it is living
Change is handled.It is preceding to prototype immersion treatment to change plating, the preparation before completionization plating.
The stable treatment formulations of the prototype of table 2
| Component | Temperature | Time |
| The aqueous solution of formaldehyde 10% | Room temperature | 1min |
(3) electroless copper：It is preferred that with chemical plating formula shown in table 3, by chemical reaction, in the table of prototype activating area
Face forms conductive copper layer.Preferably, reaction temperature is 20~25 DEG C, and the reaction time is 45~60nin.
The prototype electroless copper treatment formulations of table 3
| Component | Content |
| Copper sulphate | 10g/L |
| Potassium sodium tartrate | 50g/L |
| Sodium hydroxide | 10~12g/L |
| Sodium carbonate | 5g/L |
| Nickel chloride | 1g/L |
| Formaldehyde | 10~15ml/L |
Step 5, surface post processing.
By the link of chemical plating, prototype surface forming surface conductance circuit.Can be respective according to circuit
Performance requirement, row line validity test is entered to it.Surface post processing can be carried out by the prototype of test, clear up line layer surface
Impurity, reduce its surface roughness.In order to which protection circuit is not easy destroyed and prevents the oxidation of surface copper clad layers, preferably in prototype
Part copper plate surface spraying protects solution, is finally completed the making of MID devices.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (9)
1. a kind of preparation method of stereo circuit, it is characterised in that comprise the following steps：
Step 1: prototype is generated by selective laser sintering method；
Step 2: spray treatment is carried out to the prototype surface with the thermosetting spray solution containing soluble metal complex compound
And solidify, forming surface can be by the overlay film of laser activation；
Step 3: predetermined selective scanning is carried out to the overlay film to form surface active region with laser；
Step 4: conducting wire is formed in the surface active region by chemical plating；
In the step 1, the carbon dioxide infrared laser for using wavelength to be 10W~40W for 10.6 μm, power is selected
Property laser sintered, wherein 3~5m/s of laser scan rate, spot diameter 0.5mm, X, Y, Z axis processing shrinkage-compensating rate X is 2.85
~3.82%, Y is 2.85~3.82%, Z (0) is 2.10~3.22%, Z (300) is 1.47~2.44%, and wherein Z (0) refers to
The shrinkage-compensating rate of Z axis coordinate 0mm positions, Z (300) refer to the shrinkage-compensating rate in Z axis coordinate 300mm positions, Z-direction remainder layer
Shrinkage factor is distributed according to Z (0), Z (300) value linearly rule of constant concentration, and laser facula compensating parameter is 0.15~0.35mm.
2. preparation method as claimed in claim 1, it is characterised in that the thermosetting spray solution in parts by mass contain with
Lower composition：(1) mass parts of thermoset carrier rubber master batch 35~65；(2) mass parts of amino resins 15~30；(3) metal complex 0.5
~10 mass parts；(4) mass parts of inorganic functional fillers 15~25；(5) mass parts of aromatic solvent 3~5；(6) DAA 3~5
Mass parts；(7) mass parts of dimethylbenzene 2~4；(8) mass parts of defoamer 0.1~0.7；(9) mass parts of dispersant 0.1~2；(10)
The mass parts of levelling agent 0.1~1.
3. preparation method as claimed in claim 1, it is characterised in that the metal complex is the complexing of copper, aluminium, zinc or nickel
Thing.
4. the preparation method as described in any one of claims 1 to 3, it is characterised in that in the step 3, use power as 10
The laser equipment that~40W, wavelength are 10.6 μm of laser equipment or power is 3~10W, wavelength is 1060~1090nm is swashed
Optical scanning, line width 0.1mm, minimum spacing 0.2mm.
5. preparation method as claimed in claim 4, it is characterised in that the laser equipment has X/Y scanning galvanometers and setting
Into varifocal on the Z axis perpendicular to surface to be activated.
6. preparation method as claimed in claim 4, it is characterised in that in the step 3, surface laser is activated to the original
The recession thickness of airfoil surface is maintained at 20~25 μm.
7. the preparation method as described in any one of claims 1 to 3, it is characterised in that in the step 4, carrying out chemical plating
Also include carrying out the surface of the prototype oil removing and immersion stabilization processing before, the stable processing of immersion, which uses, contains 10%
The aqueous solution of formaldehyde, soaks 1min at room temperature.
8. preparation method as claimed in claim 7, it is characterised in that the oil removing removes oil formula, wherein hydrogen-oxygen using following
Change sodium 100g/L, tertiary sodium phosphate 166.6g/L, sodium carbonate 100g/L, and detergent 16.6g/L.
9. the preparation method as described in any one of claims 1 to 3, it is characterised in that chemical plating uses following electroplate liquid formulation, its
In contain copper sulphate 10g/L, potassium sodium tartrate 50g/L, 10~12g/L of sodium hydroxide, sodium carbonate 5g/L, nickel chloride 1g/L, with
And 10~15ml/L of formaldehyde.
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| CN109988454A (en) * | 2017-12-29 | 2019-07-09 | 戴春东 | A kind of laser activation ink and preparation method thereof for making mobile phone stereo circuit |
| CN108925055A (en) * | 2018-07-02 | 2018-11-30 | 上海安费诺永亿通讯电子有限公司 | A method of the generative circuit on 3D bend glass |
| CN110868815B (en) * | 2019-11-15 | 2021-08-13 | 航天恒星科技有限公司 | Curved surface three-dimensional circuit board preparation method and curved surface three-dimensional circuit board |
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| DE19723734C2 (en) * | 1997-06-06 | 2002-02-07 | Gerhard Naundorf | Conductor structures on a non-conductive carrier material and method for their production |
| ATE279552T1 (en) * | 2000-09-26 | 2004-10-15 | Enthone Omi Deutschland Gmbh | METHOD FOR SELECTIVE METALLIZATION OF DIELECTRIC MATERIALS |
| US20060003262A1 (en) * | 2004-06-30 | 2006-01-05 | Eastman Kodak Company | Forming electrical conductors on a substrate |
| CN101859613B (en) * | 2009-04-09 | 2013-03-27 | 深圳市微航磁电技术有限公司 | Three-dimensional circuit manufacturing process and composite components of laser plastic material and manufacturing method |
| CN102242354A (en) * | 2011-05-26 | 2011-11-16 | 深圳市泛友科技有限公司 | Selective chemical plating process and corresponding laser coatings and preparation method thereof |
| CN102905473B (en) * | 2011-07-29 | 2017-06-06 | 富泰华工业（深圳）有限公司 | The preparation method of circuit board and circuit board |
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